Nanocrystalline Quantum Dot Heterostructure

ABSTRACT

A semiconductor structure includes a nanocrystalline core comprising a first semiconductor material having a first bandgap, and a nanocrystalline shell comprising a second semiconductor material different than the first semiconductor material at least partially surrounding the nanocrystalline core, the second semiconductor material having a second bandgap greater than the first bandgap.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/188,321, filed Jul. 2, 2015, the entire contents of which are herebyincorporated by reference herein.

TECHNICAL FIELD

Embodiments of the invention relate to the field of quantum dots forlight emitting diodes (LEDs) and other applications and, in particular,a seeded semiconductor rod structure to optimize the functions ofabsorption and emission of light in a nanocrystalline quantum dot.

BACKGROUND

Quantum dots having a high photoluminescence quantum yield (PLQY) may beapplicable as down-converting materials in down-convertingnanocomposites used in solid state lighting applications.Down-converting materials are used to improve the performance,efficiency and color choice in lighting applications, particularly lightemitting diodes (LEDs). In such applications, quantum dots absorb lightof a particular first (available or selected) wavelength, usually blue,and then emit light at a second wavelength, usually red or green.

SUMMARY

According to embodiments of the invention, a quantum dot includes ananocrystalline core and an alloyed nanocrystalline shell made of asemiconductor material composition different from the nanocrystallinecore. The alloyed nanocrystalline shell is bonded to and completelysurrounds the nanocrystalline core.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a plot of prior art core/shell absorption (left y-axis)and emission spectra intensity (right y-axis) as a function ofwavelength for conventional quantum dots.

FIG. 2 illustrates a schematic of a cross-sectional view of a quantumdot, in accordance with an embodiment of the invention.

FIG. 3 illustrates a schematic of an integrating sphere for measuringabsolute photoluminescence quantum yield, in accordance with anembodiment of the invention.

FIG. 4 is a plot of photon counts as a function of wavelength innanometers for sample and reference emission spectra used in themeasurement of photoluminescence quantum yield, in accordance with anembodiment of the invention.

FIG. 5 is a plot including a UV-Vis absorbance spectrum andphotoluminescent emission spectrum for red CdSe/CdS core/shell quantumdots, in accordance with an embodiment of the invention.

FIG. 6 is a plot including a UV-Vis absorbance spectrum andphotoluminescent emission spectrum for a green CdSe/CdS core/shellquantum dot, in accordance with an embodiment of the invention.

FIG. 7 illustrates operations in a reverse micelle approach to coating asemiconductor structure, in accordance with an embodiment of theinvention.

FIG. 8 is a transmission electron microscope (TEM) image of silicacoated CdSe/CdS core/shell quantum dots having complete silicaencapsulation, in accordance with an embodiment of the invention.

FIGS. 9A-9C illustrate schematic representations of possible compositecompositions for quantum dot integration, in accordance with anembodiment of the invention.

FIG. 10 is a transmission electron microscope (TEM) image of a sample ofcore/shell CdSe/CdS quantum dots, in accordance with an embodiment ofthe invention.

FIG. 11 is a plot including a UV-Vis absorbance spectrum andphotoluminescent emission spectrum for a CdSe/CdS core/shell quantum dothaving a PLQY of 96%, in accordance with an embodiment of the invention.

FIG. 12 is a transmission electron microscope (TEM) image of a sample ofCdSe/CdS quantum dots having a PLQY of 96%, in accordance with anembodiment of the invention.

FIG. 13 is a plot of CdSe QD band edge absorption versus (CdSe)CdS(QD)QR centroid emission, in accordance with an embodiment of theinvention.

FIG. 14A is a schematic illustrating emission wavelength (nm) decreaseas a function of energy increase, in accordance with an embodiment ofthe invention.

FIG. 14B is a schematic illustrating emission wavelength (nm) decreaseas a function of energy increase, in accordance with another embodimentof the invention.

FIG. 15 includes a UV-Vis spectrum of CdSeS QDs with λ_(max) atapproximately 464.7 nm and a UV-Vis spectrum of CdSeS QDs with λ_(max)at approximately 476.2 nm, in accordance with an embodiment of thepresent invention.

FIG. 16 includes a transmission electron microscope (TEM) image and aTEM image comparing CdSe QDs and CdSeS QDs, respectively, in accordancewith an embodiment of the present invention.

FIG. 17 includes a TEM image and a TEM image comparing CdSe QDs andCdSeS QDs, respectively, in accordance with another embodiment of thepresent invention.

FIG. 18 is a plot showing transmission spectroscopy curves for alloyednanocrystals, in accordance with an embodiment of the present invention.

FIG. 19 illustrates a Type I heterostructure using binary semiconductorsfor a nanocrystalline core, a nanocrystalline shell, and ananocrystalline outer shell, in which transition to Type IIheterostructure occurs around 594 nm.

FIG. 20 illustrates a Type I heterostructure using ternarysemiconductors for a nanocrystalline core and nanocrystalline shell, inwhich transition to a Type II heterostructure occurs around 490 nm.

FIG. 21 illustrates a ternary semiconductor nanocrystalline shellsurrounding a binary or ternary semiconductor nanocrystalline core inaccordance with an embodiment of the present invention.

FIG. 22 includes TEM images comparing a ternary CdZnS shell on a binaryCdSe core to a ternary CdZnS shell on a ternary CdSeS core, according toembodiments of the present invention.

FIG. 23 illustrates a desired Type-I bandgap heterojunction versus anundesired Type-II bandgap heterojunction in connection with anembodiment of the invention.

FIG. 24 illustrates a ternary semiconductor nanocrystalline shellsurrounding a binary or ternary semiconductor nanocrystalline core inaccordance with an embodiment of the invention.

DETAILED DESCRIPTION

Alloyed nanocrystals and quantum dots having alloyed nanocrystals aredescribed herein. In the following description, numerous specificdetails are set forth, such as specific quantum dot compositions,geometries and efficiencies, in order to provide a thoroughunderstanding of embodiments of the invention. It will be apparent toone skilled in the art that embodiments of the invention may bepracticed without these specific details. In other instances, well-knownrelated apparatuses, such as the host of varieties of applicable lightemitting diodes (LEDs), are not described in detail in order to notunnecessarily obscure embodiments of the invention. Furthermore, it isto be understood that the various embodiments shown in the figures areillustrative representations and are not necessarily drawn to scale.

Disclosed herein are quantum dots having high photoluminescence quantumyields (PLQY's) and methods of making and encapsulating such quantumdots. A high PLQY is achieved by using a synthetic process thatsignificantly reduces the defects and self absorption found in prior artquantum dots. The resulting geometries of the quantum dots may includespherical, prolate spheroidal, and/or ellipsoidal quantum dot coressurrounded with a rod-shaped shell. The aspect or volume ratio of the(core)shell pairing may be controlled by monitoring the reaction processused to fabricate the pairing. Uses of quantum dot compositions havinghigh PLQYs are also disclosed, including solid state lighting. Otherapplications include biological imaging and fabrication of photovoltaicdevices. In other embodiments, alloyed nanocrystals are incorporated asnanocrystalline cores for quantum dots based on heterostructures.

As a reference point, quantum dots based on a spherical cadmium selenide(CdSe) core embedded in a cadmium sulfide (CdS) nanorod shell have beenreported. Such quantum dots do not have a high PLQY. Typically, priorart core/shell quantum dots suffer from several structural deficiencieswhich may contribute to a reduced PLQY. For example, prior artcore/shell quantum dots used for down-shifting applications typicallyhave overlapping absorption and emission profiles. Profile overlap maybe attributed to core material selection such that both the absorptionand emission of the quantum dot is controlled by the size, shape, andcomposition of the core quantum dot, and the shell, if any, is used onlyas a passivating layer for the surface. However, the prior artarrangement leads to a significant amount of self-absorption(re-absorption of the down-shifted light), which decreases the measuredPLQY. Accordingly, a typical prior art core/shell quantum dot PLQY isbelow 80% which is often not high enough for device applications. Also,prior art core/shell quantum dots suffer from self absorption due inpart to inappropriate volume of core/shell material.

As an example, FIG. 1 depicts a plot 100 of prior art core/shellabsorption and emission spectra intensity as a function of wavelengthfor conventional quantum dots. The absorption spectra (102 a, 102 b, 102c) are of CdSe core nanorods for a same core size with differentthickness shells (a, b, c). FIG. 1 also depicts the emission spectra(104 a, 104 b, 104 c) of the three core/shell quantum dots afterexposure to laser light. The absorption spectrum and the emissionspectrum overlap for each thickness of shell.

The low PLQY of prior art quantum dots is also attributed to poornanocrystal surface and crystalline quality. The poor quality may resultfrom a previous lack of capability in synthetic techniques for treatingor tailoring the nanocrystal surface in order to achieve PLQYs above 90percent. For example, the surface may have a large number of danglingbonds which act as trap states to reduce emission and, hence, PLQY.Previous approaches to address such issues have included use of a verythin shell, e.g., approximately ½ monolayer to 5 monolayers, or up toabout 1.5 nm of thickness, to preserve the epitaxial nature of theshell. However, a PLQY of only 50-80% has been achieved. In suchsystems, considerable self-absorption may remain, decreasing the PLQY inmany device applications. Other approaches have included attempts togrow a very large volume of up to 19 monolayers, or about 6 nm of shellmaterial on a nanometer-sized quantum dot. However, the results havebeen less than satisfactory due to mismatched lattice constants betweenthe core and shell material.

Conventionally, a spherical shell is grown on a spherical core in orderto fabricate a core/shell quantum dot system. However, if too muchvolume of shell material is added to the core, the shell often will tocrack due to strain. The strain introduces defects and decreases thePLQY. Band-edge emission from the quantum dots is then left to competewith both radiative and non-radiative decay channels, originating fromdefect electronic states. Attempts have been made to use an organicmolecule as a passivating agent in order to improve the size-dependentband-edge luminescence efficiency, while preserving the solubility andprocessability of the particles. Unfortunately, however, passivation byway of organic molecule passivation is often incomplete or reversible,exposing some regions of the surface of a quantum dot to degradationeffects such as photo-oxidation. In some cases, chemical degradation ofthe ligand molecule itself or its exchange with other ligands results infabrication of poor quality quantum dots.

One or more embodiments of the invention address at least one or more ofthe above issues regarding quantum dot quality and behavior and theimpact on PLQY of the fabricated quantum dots. In one approach, thequality of quantum dot particle interfaces is improved over conventionalsystems. For example, in one embodiment, high PLQY temperature stabilityof a fabricated (e.g., grown) quantum dot is centered on the passivationor elimination of internal (at the seed/rod interface) and external (atthe rod surface) interface defects that provide non-radiativerecombination pathways for electron-hole pairs that otherwise competewith a desirable radiative recombination. This approach may be generallycoincident with maximizing the room-temperature PLQY of the quantum dotparticles. Thus, thermal escape paths from the quantum dot, assisted byquantum dot phonons, are mitigated as a primary escape mechanism forthermally excited carriers. Although the chemical or physical nature ofsuch trap states has not been phenomenologically explored, suitablytuning electron density at the surface may deactivate trap states. Suchpassivation is especially important at increased temperatures, wherecarriers have sufficient thermal energy to access a larger manifold ofthese states.

In an embodiment, approaches described herein exploit the concept oftrap state deactivation. Furthermore, maintenance of such a deactivationeffect over time is achieved by insulating a quantum dot interfaceand/or outer most surface from an external environment. The deactivationof surface states is also important for the fabrication of polymercomposites including quantum dots, particularly in the case where thepolymer composite is exposed to a high flux light-source (as is the casefor solid state lighting (SSL)) where it is possible for some of theparticles to have more than one exciton. The multi-excitons mayrecombine radiatively or non-radiatively via Auger recombination to asingle exciton state. For non-passivated quantum dot systems, the Augerrate increases with particle volume and with exciton population.However, in an embodiment, a thick, high quality, asymmetric shell of(e.g., of CdS) is grown on well-formed seeds (e.g., CdSe) to mitigateAuger rate increase.

One or more embodiments described herein involve an optimized synthesisof core/shell quantum dots. In a specific example, high PLQY andtemperature stable quantum dots are fabricated from CdSe/CdS core-shellnanorods. In order to optimize the quantum dots in place of lightemitting diode (LED) phosphors, the temperature stability of the quantumdots is enhanced, and the overall PLQY increased. Such improvedperformance is achieved while maintaining high absorption and narrowemission profiles for the quantum dots. In one such embodiment,materials systems described herein are tailored for separateoptimization of absorption and emission by employing a core/shellstructure. The core material predominantly controls the emission and theshell material predominantly controls the absorption. The describedsystems enable separate optimization of absorption and emission andprovides very little overlap of the absorption and emission to minimizere-absorption of any emitted light by the quantum dot material (i.e.,self-absorption).

Several factors may be intertwined for establishing an optimizedgeometry for a quantum dot having a nanocrystalline core andnanocrystalline shell pairing. As a reference, FIG. 2 illustrates aschematic of a cross-sectional view of a quantum dot, in accordance withan embodiment of the invention. Referring to FIG. 2, a semiconductorstructure (e.g., a quantum dot structure) 200 includes a nanocrystallinecore 202 surrounded by a nanocrystalline shell 204. The nanocrystallinecore 202 has a length axis (a_(CORE)), a width axis (b_(CORE)) and adepth axis (c_(CORE)), the depth axis provided into and out of the planeshown in FIG. 2. Likewise, the nanocrystalline shell 204 has a lengthaxis (a_(SHELL)), a width axis (b_(SHELL)) and a depth axis (c_(SHELL)),the depth axis provided into and out of the plane shown in FIG. 2. Thenanocrystalline core 202 has a center 203 and the nanocrystalline shell204 has a center 205. The nanocrystalline shell 204 surrounds thenanocrystalline core 202 in the b-axis direction by an amount 206, as isalso depicted in FIG. 2.

In an embodiment, the nanocrystalline shell 204 completely surrounds thenanocrystalline core 202, as depicted in FIG. 2. In an alternativeembodiment, however, the nanocrystalline shell 204 only partiallysurrounds the nanocrystalline core 202, exposing a portion of thenanocrystalline core 202. Furthermore, in either case, thenanocrystalline core 202 may be disposed in an asymmetric orientationwith respect to the nanocrystalline shell 204. In one or moreembodiments, semiconductor structures such as 200 are fabricated tofurther include a nanocrystalline outer shell 210 at least partiallysurrounding the nanocrystalline shell 204. The nanocrystalline outershell 210 may be composed of a third semiconductor material differentfrom the first and second semiconductor materials, i.e., different fromthe materials of the core 202 and shell 204. The nanocrystalline outershell 210 may completely surround the nanocrystalline shell 204 or mayonly partially surround the nanocrystalline shell 204, exposing aportion of the nanocrystalline shell 204. Additional nanocrystallineshells may also be formed that partially or completely surround thecore/shell(s) pairing, further improving the stability of thesemiconductor material, for example, by reducing degradation due toemission over time.

The following are attributes of a quantum dot that may be tuned foroptimization, with reference to the parameters provided in FIG. 2, inaccordance with embodiments of the invention. Nanocrystalline core 202diameter (a, b or c) and aspect ratio (e.g., a/b) can be controlled forrough tuning for emission wavelength (a higher value for eitherproviding increasingly red emission). A smaller overall nanocrystallinecore provides a greater surface to volume ratio. The width of thenanocrystalline shell along 206 may be tuned for yield optimization andquantum confinement providing approaches to control red-shifting andmitigation of surface effects. However, strain considerations must beaccounted for when optimizing the value of thickness 206. The length(a_(SHELL)) of the shell is tunable to provide longer radiative decaytimes as well as increased light absorption. The overall aspect ratio ofthe structure 200 (e.g., the greater of a_(SHELL)/b_(SHELL) anda_(SHELL)/c_(SHELL)) may be tuned to directly impact PLQY. Meanwhile,overall surface/volume ratio for 200 may be kept relatively smaller toprovide lower surface defects, provide higher photoluminescence, andlimit self-absorption. Referring again to FIG. 2, the shell/coreinterface 208 may be tailored to avoid dislocations and strain sites. Inone such embodiment, a high quality interface is obtained by tailoringone or more of injection temperature and mixing parameters, the use ofsurfactants, and control of the reactivity of precursors, as isdescribed in greater detail below.

In accordance with an embodiment of the invention, a high PLQY quantumdot is based on a core/shell pairing using an anisotropic core. Withreference to FIG. 2, an anisotropic core is a core having one of theaxes a_(CORE), b_(CORE) or c_(CORE) different from one or both of theremaining axes. An aspect ratio of such an anisotropic core isdetermined by the longest of the axes a_(CORE), b_(CORE) or c_(CORE)divided by the shortest of the axes a_(CORE), b_(CORE) or c_(CORE) toprovide a number greater than 1 (an isotropic core has an aspect ratioof 1). It is to be understood that the outer surface of an anisotropiccore may have rounded or curved edges (e.g., as in an ellipsoid) or maybe faceted (e.g., as in a stretched or elongated tetragonal or hexagonalprism) to provide an aspect ratio of greater than 1 (note that a sphere,a tetragonal prism, and a hexagonal prism are all considered to have anaspect ratio of 1 in keeping with embodiments of the invention).

A workable range of aspect ratio for an anisotropic nanocrystalline corefor a quantum dot may be selected for maximization of PLQY. For example,a core essentially isotropic may not provide advantages for increasingPLQY, while a core with too great an aspect ratio (e.g., 2 or greater)may present challenges synthetically and geometrically when forming asurrounding shell. Furthermore, embedding the core in a shell composedof a material different than the core may also be used enhance PLQY of aresulting quantum dot.

With reference to the above described nanocrystalline core andnanocrystalline shell pairings, in an embodiment, the nanocrystallineshell completely surrounds the anisotropic nanocrystalline core. In analternative embodiment, however, the nanocrystalline shell onlypartially surrounds the anisotropic nanocrystalline core, exposing aportion of the anisotropic nanocrystalline core, e.g., as in a tetrapodgeometry or arrangement. In an embodiment, the nanocrystalline shell isan anisotropic nanocrystalline shell, such as a nano-rod, that surroundsthe anisotropic nanocrystalline core at an interface between theanisotropic nanocrystalline shell and the anisotropic nanocrystallinecore. The anisotropic nanocrystalline shell passivates or reduces trapstates at the interface. The anisotropic nanocrystalline shell may also,or instead, deactivate trap states at the interface.

With reference again to the above described nanocrystalline core andnanocrystalline shell pairings, in an embodiment, the first and secondsemiconductor materials (core and shell, respectively) are eachmaterials such as, but not limited to, Group II-VI materials, GroupIII-V materials, Group IV-VI materials, Group materials, or GroupII-IV-VI materials and, in one embodiment, are monocrystalline. In onesuch embodiment, the first and second semiconductor materials are bothGroup II-VI materials, the first semiconductor material is cadmiumselenide (CdSe), and the second semiconductor material is one such as,but not limited to, cadmium sulfide (CdS), zinc sulfide (ZnS), or zincselenide (ZnSe). In one embodiment either or both of the first andsecond semiconductor materials include a Magnesium Chalcogenide andalloyed Group II-VI materials. In an embodiment, the semiconductorstructure further includes a nanocrystalline outer shell at leastpartially surrounding the nanocrystalline shell and, in one embodiment,the nanocrystalline outer shell completely surrounds the nanocrystallineshell. The nanocrystalline outer shell is composed of a thirdsemiconductor material different from the first and second semiconductormaterials. In a particular such embodiment, the first semiconductormaterial is cadmium selenide (CdSe), the second semiconductor materialis cadmium sulfide (CdS), and the third semiconductor material is zincsulfide (ZnS). In another embodiment, the first semiconductor materialis a Group II-VI material, the second semiconductor material includes amagnesium chalcogenide alloyed with Group II-VI materials, and the thirdsemiconductor material is zinc magnesium sulfide (ZnMgS). In anotherembodiment, the first semiconductor material is cadmium selenide sulfide(CdSeS), the second semiconductor material is cadmium zinc sulfide(CdZnS), and the third semiconductor material is zinc magnesium sulfide(ZnMgS).

With reference again to the above described nanocrystalline core andnanocrystalline shell pairings, in an embodiment, the semiconductorstructure (i.e., the core/shell pairing in total) has an aspect ratioapproximately in the range of 1.5-10 and, 3-6 in a particularembodiment. In an embodiment, the nanocrystalline shell has a long axisand a short axis. The long axis has a length approximately in the rangeof 5-40 nanometers. The short axis has a length approximately in therange of 1-10 nanometers greater than a diameter of the anisotropicnanocrystalline core parallel with the short axis of the nanocrystallineshell. In a specific such embodiment, the anisotropic nanocrystallinecore has a diameter approximately in the range of 2-5 nanometers. Inanother embodiment, the anisotropic nanocrystalline core has a diameterapproximately in the range of 2-5 nanometers. The thickness of thenanocrystalline shell on the anisotropic nanocrystalline core along ashort axis of the nanocrystalline shell is approximately in the range of1-5 nanometers of the second semiconductor material.

In yet another embodiment, the anisotropic nanocrystalline core has adiameter approximately in the range of 4 nm along its short axis. Thelong axis of a rod-shaped nanocrystalline shell encompassing the corehas a length approximately in the range of 15-25 nanometers, and theshell has a length approximately in the range of 2-3 nanometers greaterthan a diameter of the anisotropic nanocrystalline core parallel withthe short axis of the nanocrystalline shell.

With reference again to the above-described nanocrystalline core andnanocrystalline shell pairings, in an embodiment, the anisotropicnanocrystalline core and the nanocrystalline shell form a quantum dot.In one such embodiment, the quantum dot has a photoluminescence quantumyield (PLQY) of at least 90%. Emission from the quantum dot may bemostly, or entirely, from the nanocrystalline core. For example, in anembodiment, emission from the anisotropic nanocrystalline core is atleast approximately 75% of the total emission from the quantum dot. Anabsorption spectrum and an emission spectrum of the quantum dot may beessentially non-overlapping. For example, in an embodiment, anabsorbance ratio of the quantum dot based on absorbance at 400nanometers versus absorbance at an exciton peak for the quantum dot isapproximately in the range of 5-35.

In an embodiment, a quantum dot based on the above describednanocrystalline core and nanocrystalline shell pairings is adown-converting quantum dot. However, in an alternative embodiment, thequantum dot is an up-shifting quantum dot. In either case, a lightingapparatus may include a light emitting diode and a plurality of quantumdots such as those described above. The quantum dots may be appliedproximal to the LED and provide down-conversion or up-shifting of lightemitted from the LED. Thus, semiconductor structures according to theinvention may be advantageously used in solid state lighting. Thevisible spectrum includes light of different colors having wavelengthsbetween about 380 nm and about 780 nm that are visible to the human eye.An LED will emit a UV or blue light which is down-converted (orup-shifted) by semiconductor structures described herein. Any suitableratio of color semiconductor structures may be used in devices of theinvention. LED devices according to embodiments of the invention mayhave incorporated therein sufficient quantity of semiconductorstructures (e.g., quantum dots) described herein capable ofdown-converting any available blue light to red, green, yellow, orange,blue, indigo, violet or other color.

Semiconductor structures according to embodiments of the invention maybe advantageously used in biological imaging in, e.g., one or more ofthe following environments: fluorescence resonance energy transfer(FRET) analysis, gene technology, fluorescent labeling of cellularproteins, cell tracking, pathogen and toxin detection, in vivo animalimaging or tumor biology investigation. Accordingly, embodiments of theinvention contemplate probes having quantum dots described herein.

Semiconductor structures according to embodiments of the invention maybe advantageously used in photovoltaic cells in layers where high PLQYis important. Accordingly, embodiments of the invention contemplatephotovoltaic devices using quantum dots described herein.

There are various synthetic approaches for fabricating CdSe quantumdots. For example, in an embodiment, under an inert atmosphere (e.g.,ultra high purity (UHP) argon), cadmium oxide (CdO) is dissociated inthe presence of surfactant (e.g., octadecylphosphonic acid (ODPA)) andsolvent (e.g., trioctylphosphine oxide (TOPO); trioctylphosphine (TOP))at high temperatures (e.g., 350-380 degrees Celsius). Resulting Cd²⁺cations are exposed by rapid injection to solvated selenium anions(Se²⁻), resulting in a nucleation event forming small CdSe seeds. Theseeds continue to grow, feeding off of the remaining Cd²⁺ and Se²⁻available in solution, with the resulting quantum dots being stabilizedby surface interactions with the surfactant in solution (ODPA). Theaspect ratio of the CdSe seeds is typically between 1 and 2, as dictatedby the ratio of the ODPA to the Cd concentration in solution. Thequality and final size of these cores is affected by several variablessuch as, but not limited to, reaction time, temperature, reagentconcentration, surfactant concentration, moisture content in thereaction, or mixing rate. The reaction is targeted for a narrow sizedistribution of CdSe seeds (assessed by transmission electron microscopy(TEM)), typically a slightly cylindrical seed shape (also assessed byTEM) and CdSe seeds exhibiting solution stability over time (assessed byPLQY and scattering in solution).

For the cadmium sulfide (CdS) shell growth on the CdSe seeds, ornanocrystalline cores, under an inert atmosphere (e.g. UHP argon),cadmium oxide (CdO) is dissociated in the presence of surfactants (e.g.,ODPA and hexylphosphonic acid (HPA)) and solvent (e.g. TOPO and/or TOP)at high temperatures (e.g., 350-380 degrees Celsius). The resulting Cd²⁺cations in solution are exposed by rapid injection to solvated sulfuranions (S²⁻) and CdSe cores. Immediate growth of the CdS shell aroundthe CdSe core occurs. The use of both a short chain and long chainphosphonic acid promotes enhanced growth rate at along the c-axis of thestructure, and slower growth along the a-axis, resulting in a rod-shapedcore/shell nanomaterial.

CdSe/CdS core-shell quantum dots have been shown in the literature toexhibit respectable quantum yields (e.g., 70-75%). However, thepersistence of surface trap states (which decrease overallphotoluminescent quantum yield) in these systems arises from a varietyof factors such as, but not limited to, strain at the core-shellinterface, high aspect ratios (ratio of rod length to rod width of thecore/shell pairing) which lead to larger quantum dot surface arearequiring passivation, or poor surface stabilization of the shell.

In order to address the above synthetic limitations on the quality ofquantum dots formed under conventional synthetic procedures, in anembodiment, a multi-faceted approach is used to mitigate or eliminatesources of surface trap states in quantum dot materials. For example,lower reaction temperatures during the core/shell pairing growth yieldsslower growth at the CdSe—CdS interface, giving each material sufficienttime to orient into the lowest-strain positions. Aspect ratios arecontrolled by changing the relative ratios of surfactants in solution aswell as by controlling temperature. Increasing an ODPA/HPA ratio inreaction slows the rapid growth at the ends of the core/shell pairingsby replacing the facile HPA surfactant with the more obstructive ODPAsurfactant. In addition, lowered reaction temperatures are also used tocontribute to slowed growth at the ends of the core/shell pairings. Bycontrolling these variables, the aspect ratio of the core/shell pairingis optimized for quantum yield. In one such embodiment, followingdetermination of optimal surfactant ratios, overall surfactantconcentrations are adjusted to locate a PLQY maximum while maintaininglong-term stability of the fabricated quantum dots in solution.Furthermore, in an embodiment, aspect ratios of the seed or core (e.g.,as opposed to the seed/shell pairing) are limited to a range between,but not including 1.0 and 2.0 in order to provide an appropriategeometry for high quality shell growth thereon.

In another aspect, an additional or alternative strategy for improvingthe interface between CdSe and CdS includes, in an embodiment,chemically treating the surface of the CdSe cores prior to reaction.CdSe cores are stabilized by long chain surfactants (ODPA) prior tointroduction into the CdS growth conditions. Reactive ligand exchangecan be used to replace the ODPA surfactants with ligands which areeasier to remove (e.g., primary or secondary amines), facilitatingimproved reaction between the CdSe core and the CdS growth reagents.

In addition to the above factors affecting PLQY in solution,self-absorption may negatively affect PLQY when these materials are castinto films. This phenomenon may occur when CdSe cores re-absorb lightemitted by other quantum dots. In one embodiment, the thickness of theCdS shells around the same CdSe cores is increased in order to increasethe amount of light absorbed per core/shell pairing, while keeping theparticle concentration the same or lower in films including the quantumdot structures. The addition of more Cd and S to the shell formationreaction leads to more shell growth, while an optimal surfactant ratioallows targeting of a desired aspect ratio and solubility of thecore/shell pairing.

Accordingly, in an embodiment, an overall method of fabricating asemiconductor structure, such as the above described quantum dotstructures, includes forming an anisotropic nanocrystalline core from afirst semiconductor material. A nanocrystalline shell is formed from asecond, different, semiconductor material to at least partially surroundthe anisotropic nanocrystalline core. In one such embodiment, theanisotropic nanocrystalline core has an aspect ratio between, but notincluding, 1.0 and 2.0, as described above.

With reference to the above described general method for fabricating ananocrystalline core and nanocrystalline shell pairing, in anembodiment, prior to forming the nanocrystalline shell, the anisotropicnanocrystalline core is stabilized in solution with a surfactant. In onesuch embodiment, the surfactant is octadecylphosphonic acid (ODPA). Inanother such embodiment, the surfactant acts as a ligand for theanisotropic nanocrystalline core. In that embodiment, the method furtherincludes, prior to forming the nanocrystalline shell, replacing thesurfactant ligand with a second ligand, the second ligand more labilethan the surfactant ligand. In a specific such embodiment, the secondligand is one such as, but not limited to, a primary amine or asecondary amine.

With reference again to the above described general method forfabricating a nanocrystalline core and nanocrystalline shell pairing, inan embodiment, forming the nanocrystalline shell includes forming thesecond semiconductor material in the presence of a mixture ofsurfactants. In one such embodiment, the mixture of surfactants includesa mixture of octadecylphosphonic acid (ODPA) and hexylphosphonic acid(HPA). In a specific such embodiment, forming the nanocrystalline shellincludes tuning the aspect ratio of the nanocrystalline shell by tuningthe ratio of ODPA versus HPA. Forming the second semiconductor materialin the presence of the mixture of surfactants may also, or instead,include using a solvent such as, but not limited to, trioctylphosphineoxide (TOPO) and trioctylphosphine (TOP).

With reference again to the above described general method forfabricating a nanocrystalline core and nanocrystalline shell pairing, inan embodiment, forming the anisotropic nanocrystalline core includesforming at a temperature approximately in the range of 350-380 degreesCelsius. In an embodiment, forming the anisotropic nanocrystalline coreincludes forming a cadmium selenide (CdSe) nanocrystal from cadmiumoxide (CdO) and selenium (Se) in the presence of a surfactant at atemperature approximately in the range of 300-400 degrees Celsius. Thereaction is arrested prior to completion. In one such embodiment,forming the nanocrystalline shell includes forming a cadmium sulfide(CdS) nanocrystalline layer on the CdSe nanocrystal from cadmium oxide(CdO) and sulfur (S) at a temperature approximately in the range of120-380 degrees Celsius. That reaction is also arrested prior tocompletion.

The aspect ratio of the fabricated semiconductor structures may becontrolled by one of several methods. For example, ligand exchange maybe used to change the surfactants and/or ligands and alter the growthkinetics of the shell and thus the aspect ratio. Changing the coreconcentration during core/shell growth may also be exploited. Anincrease in core concentration and/or decrease concentration ofsurfactants results in lower aspect ratio core/shell pairings.Increasing the concentration of a shell material such as S for CdS willincrease the rate of growth on the ends of the core/shell pairings,leading to longer, higher aspect ratio core/shell pairings.

As mentioned above, in one embodiment of the invention, nanocrystallinecores undergo a reactive ligand exchange which replaces core surfactantswith ligands that are easier to remove (e.g., primary or secondaryamines), facilitating better reaction between the CdSe core and the CdSgrowth reagents. In one embodiment, cores used herein have ligands boundor associated therewith. Attachment may be by dative bonding, Van derWaals forces, covalent bonding, ionic bonding or other force or bond,and combinations thereof. Ligands used with the cores may include one ormore functional groups to bind to the surface of the nanocrystals. In aspecific such embodiment, the ligands have a functional group with anaffinity for a hydrophobic solvent.

In an embodiment, lower reaction temperatures during shell growth yieldsslower growth at the core/shell interface. While not wishing to be boundby any particular theory or principle it is believed that this methodallows both core and shell seed crystals time to orient into theirlowest-strain positions during growth. Growth at the ends of thecore/shell pairing structure is facile and is primarily governed by theconcentration of available precursors (e.g., for a shell of CdS this isCd, S:TOP). Growth at the sides of the core/shell pairings is morestrongly affected by the stabilizing ligands on the surface of thecore/shell pairing. Ligands may exist in equilibrium between thereaction solution and the surface of the core/shell pairing structure.Lower reaction temperatures may tilt this equilibrium towards moreligands being on the surface, rendering it more difficult for growthprecursors to access this surface. Hence, growth in the width directionis hindered by lower temperature, leading to higher aspect ratiocore/shell pairings.

In general consideration of the above described semiconductor or quantumdot structures and methods of fabricating such semiconductor or quantumdot structures, in an embodiment, quantum dots are fabricated to have anabsorbance in the blue or ultra-violet (V) regime, with an emission inthe visible (e.g., red, orange, yellow, green, blue, indigo and violet,but particularly red and green) regime. The above described quantum dotsmay advantageously have a high PLQY with limited self-absorption,possess a narrow size distribution for cores, provide core stabilityover time (e.g., as assessed by PLQY and scattering in solution), andexhibit no major product loss during purification steps. Quantum dotsfabricated according one or more of the above embodiments may have adecoupled absorption and emission regime, where the absorption iscontrolled by the shell and the emission is controlled by the core. Inone such embodiment, the diameter of the core correlates with emissioncolor, e.g., a core diameter progressing from 3-5.5 nanometerscorrelates approximately to a green yellow red emission progression.

With reference to the above described embodiments concerningsemiconductor structures, such as quantum dots, and methods offabricating such structures, the concept of a crystal defect, ormitigation thereof, may be implicated. For example, a crystal defect mayform in, or be precluded from forming in, a nanocrystalline core or in ananocrystalline shell, at an interface of the core/shell pairing, or atthe surface of the core or shell. In an embodiment, a crystal defect isa departure from crystal symmetry caused by one or more of freesurfaces, disorders, impurities, vacancies and interstitials,dislocations, lattice vibrations, or grain boundaries. Such a departuremay be referred to as a structural defect or lattice defect. Referenceto an exciton is to a mobile concentration of energy in a crystal formedby an excited electron and an associated hole. An exciton peak isdefined as the peak in an absorption spectrum correlating to the minimumenergy for a ground state electron to cross the bandgap. The core/shellquantum dot absorption spectrum appears as a series of overlapping peaksthat get larger at shorter wavelengths. Because of their discreteelectron energy levels, each peak corresponds to an energy transitionbetween discrete electron-hole (exciton) energy levels. The quantum dotsdo not absorb light that has a wavelength longer than that of the firstexciton peak, also referred to as the absorption onset. The wavelengthof the first exciton peak, and all subsequent peaks, is a function ofthe composition and size of the quantum dot. An absorbance ratio isabsorbance of the core/shell nanocrystal at 400 nm divided by theabsorbance of the core/shell nanocrystal at the first exciton peak.Photoluminescence quantum yield (PLQY) is defined as the ratio of thenumber of photons emitted to the number of photons absorbed. Core/shellpairing described herein may have a Type I band alignment, e.g., thecore bandgap is nested within the bandgap of the shell. Emissionwavelength may be determined by controlling the size and shape of thecore nanocrystal, which controls the bandgap of the core. Emissionwavelength may also be engineered by controlling the size and shape ofthe shell. In an embodiment, the amount/volume of shell material is muchgreater than that of the core material. Consequently, the absorptiononset wavelength is mainly controlled by the shell bandgap. Core/shellquantum dots in accordance with an embodiment of the invention have anelectron-hole pair generated in the shell which is then funneled intothe core, resulting in recombination and emission from the core quantumdot. Preferably emission is substantially from the core of the quantumdot.

Measurement of Photoluminescence Quantum Yield (PLQY) may be performedaccording to the method disclosed in Laurent Porres et al. “AbsoluteMeasurements of Photoluminescence Quantum Yields of Solutions Using anIntegrating Sphere”, Journal of Fluorescence (2006) DOI:10.1007/s10895-005-0054-8, Springer Science+Business Media, Inc. As anexample, FIG. 3 illustrates a schematic of an integrating sphere 300 formeasuring absolute photoluminescence quantum yield, in accordance withan embodiment of the invention. The integrating sphere 300 includes asample holder 302, a spectrometer 304, a calibrated light source 306 andan ultra-violet (UV) LED 308. FIG. 4 is a plot 400 of photon counts as afunction of wavelength in nanometers for sample and reference emissionspectra used in the measurement of photoluminescence quantum yield, inaccordance with an embodiment of the invention. Referring to plot 400,both excitation and emission peaks for a sample are calibrated againstcorresponding excitation and emission peaks for a reference.

In an embodiment, PLQY is measured with a Labsphere™ 6” integratingsphere, a Labsphere™ LPS-100-0105 calibrated white light source, a 3.8W, 405 nm Thorlabs™ M405L2 UV LED and an Ocean Optics™ USB4000-VIS-NIRspectrometer. The spectrometer and UV LED are coupled into the sphereusing Ocean Optics™ UV-Vis optical fibers. The spectrometer fiber isattached to a lens in a port at the side of the sphere at 90 degreesrelative to the excitation source. The lens is behind a flat baffle toensure only diffuse light reaches the lens. The calibrated white lightsource is affixed to a port in the side of the sphere, at 90° to boththe excitation source and the spectrometer port. Custom made sampleholders are used to hold solid and solution (cuvette) samples and torotate samples between direct and indirect measurement positions. Sampleholders are coated with a barium sulfate diffuse reflective material.Before measurements are recorded, the calibrated white light source isused to calibrate the spectrometer as a function of wavelength(translating counts per second into relative intensity vs. wavelength).To measure PLQY, a reference sample is inserted into the sphere, and theexcitation source LED signal is recorded. This reference sample isgenerally a blank, such as a cuvette containing a solvent or a samplewithout quantum dots, so as to only measure the properties of thequantum dots. If it is desirable to measure the properties of thematrix, the blank may be only the substrate. The sample is then insertedinto the sphere, in direct beam line for direct measurements, and out ofthe beam for indirect measurements. The spectrum is recorded and splitinto excitation and emission bands, each is integrated, and the numberof photons emitted per photons absorbed is the photoluminescence quantumyield (PLQY), which is equal to the difference between sample emissionand reference emission divided by the difference of reference excitationand sample excitation.

Quantum dots according to embodiments of the invention have a PLQYbetween 90-100%, or at least 90%, more preferably at least 91%, morepreferably at least 92%, more preferably at least 93%, more preferablyat least 94%, more preferably at least 95%, more preferably at least96%, more preferably at least 97%, more preferably at least 98%, morepreferably at least 99% and most preferably 100%. FIG. 5 is a plot 500including a UV-Vis absorbance spectrum 502 and photoluminescent emissionspectrum 504 for red CdSe/CdS core/shell quantum dots, in accordancewith an embodiment of the invention. The quantum dots have essentiallyno overlapping absorption and emission bands and having an absorbanceratio of about 24. The PLQY was determined to be 94% at 617 nm. Theaverage length (from transmission electron microscopy (TEM) data) is 27nm±3.3 nm. The average width (from TEM data) is 7.9 nm±1.1 nm. Theaverage aspect ratio (from TEM data) is 3.5±0.6. FIG. 6 is a plot 600including a UV-Vis absorbance spectrum 602 and photoluminescent emissionspectrum 604 for a green CdSe/CdS core/shell quantum dot, in accordancewith an embodiment of the invention. The quantum dot has a small extentof overlapping absorption and emission bands and has an absorbance ratioof 16 (plus or minus one).

In another aspect, semiconductor structures having a nanocrystallinecore and corresponding nanocrystalline shell and insulator coating aredescribed. Particularly, coated quantum dots structures and methods ofmaking such structures are described below. In an embodiment, core/shellquantum dots are coated with silica by a method resulting incompositions having photoluminescence quantum yields between 90 and100%. In one such embodiment, semiconductor structures are coated withsilica using a reverse micelle method. A quantum dot may be engineeredso that emission is substantially from the core.

Prior art quantum dots may have poor nanocrystal surface and crystallinequality as a result of prior art synthetic techniques not being capableof treating the nanocrystal surface in ways capable of achieving PLQYsabove 90 percent. For example, the surface of a nanocrystallinecore/shell pairing may have a large number of dangling bonds which actas trap states reducing emission and, therefore, PLQY. Prior arttechniques to modify the quantum dot surface include coating quantumdots with silica. However, prior art silica coated quantum dots do notachieve the PLQY necessary for continued use in solid state lightingdevices.

In conventional approaches, silica coatings can encapsulate more thanone particle (e.g., quantum dot structure) at a time, or the approacheshave resulted in incomplete encapsulation. One such conventionalapproach included coating a quantum dot with silica using self-assembledmicelles. The approach requires the presence of a majority of a polarsolvent to form a micelle. The requirement is for polar solventenvironments to generate the encapsulating micelle, and thus limits thetechnique to aqueous based applications, such as biological tagging andimaging. Quantum dots with a hydrophobic surfactant or ligand attachedare aqueous solution insoluble and thus silica cannot be precipitatedwith the nanocrystals within the aqueous domains of the micro emulsion.Ligand exchange reactions may be required which then leads to surfacequality degradation. However, conventional quantum dot systems oftenrely on the weak dative Van der Waals bonding of ligands such asphosphonic acids, amines, and carboxylic acids to maintain thestructures in solution and protect and passivate the surface of thequantum dot.

The integration of a quantum dot into a product may require protectionfor chemical compatibility with the solution environment duringprocessing, and ultimately the plastic or gel used for encapsulation.Without such compatibility, particles are likely to aggregate and/orredistribute themselves within the matrix, an unacceptable occurrencein, for example, a solid state lighting product. Protection of thesurface and maintenance of an electronically uniform environment alsoensures that the density of non-radiative pathways (traps) is minimized,and that the emission energy (color) is as uniform as possible.Furthermore, the surface is protected from further chemical reactionwith environmental degradants such as oxygen. This is particularlyimportant for LED applications, where the quantum dot must toleratetemperatures as high as 200 degrees Celsius and constant high-intensityillumination with high-energy light. However, the weak surface bondingof prior art quantum dot ligands are non-ideal for the processing andlong-term performance required of an LED product, as they allowdegradants access to the quantum dot surface.

In accordance with an embodiment of the invention, core/shell quantumdots coated with silica and other ligands to provide a structure havinga high PLQY. One embodiment exploits a sol-gel process whichencapsulates each quantum dot individually in a silica shell, resultingin a very stable high PLQY quantum dot particle. The coated quantum dotsdisclosed herein may advantageously possess a narrow size distributionfor CdSe core stability over time (assessed by PLQY and scattering insolution).

In a general embodiment, a semiconductor structure includes ananocrystalline core composed of a first semiconductor material. Thesemiconductor structure also includes a nanocrystalline shell composedof a second, different, semiconductor material at least partiallysurrounding the nanocrystalline core. As illustrated in FIG. 2, anadditional, outer nanocrystalline shell 210, composed of a thirdsemiconductor material, different from the second semiconductormaterial, may be formed that surrounds the core/shell pairing. Indeed,although not illustrated in FIG. 2, multiple additional shells may beformed, surrounding the core/shell(s). An insulator layer encapsulates,e.g., coats, the nanocrystalline shell(s) and nanocrystalline core.Thus, coated semiconductor structures include coated structures such asthe quantum dots described above. For example, in an embodiment, thenanocrystalline core is anisotropic, e.g., having an aspect ratiobetween, but not including, 1.0 and 2.0. In another example, in anembodiment, the nanocrystalline core is anisotropic and isasymmetrically oriented within the nanocrystalline shell. In anembodiment, the nanocrystalline core and the nanocrystalline shell(s)form a quantum dot.

With reference to the above described coated nanocrystalline core andnanocrystalline shell pairings, in an embodiment, the insulator layer isbonded directly to the nanocrystalline shell. In one such embodiment,the insulator layer passivates an outermost surface of thenanocrystalline shell. In another embodiment, the insulator layerprovides a barrier for the nanocrystalline shell and nanocrystallinecore impermeable to an environment outside of the insulator layer. Inany case, the insulator layer may encapsulate only a singlenanocrystalline shell/nanocrystalline core pairing. In an embodiment,the semiconductor structure further includes a nanocrystalline outershell at least partially surrounding the nanocrystalline shell, betweenthe nanocrystalline shell and the insulator layer. The nanocrystallineouter shell is composed of a third semiconductor material different fromthe semiconductor material of the shell and, possibly, different fromthe semiconductor material of the core.

With reference again to the above described coated nanocrystalline coreand nanocrystalline shell pairings, in an embodiment, the insulatorlayer is composed of a layer of material such as, but not limited to,silica (SiO_(x)), titanium oxide (TiO_(x)), zirconium oxide (ZrO_(x)),alumina (AlO_(x)), or hafnia (HfO_(x)). In one such embodiment, thelayer is a layer of silica having a thickness approximately in the rangeof 3-30 nanometers. In an embodiment, the insulator layer is anamorphous layer.

With reference again to the above described coated nanocrystalline coreand nanocrystalline shell pairings, in an embodiment, an outer surfaceof the insulator layer is ligand-free. However, in an alternativeembodiment, an outer surface of the insulator layer isligand-functionalized. In one such embodiment, the outer surface of theinsulator layer is ligand-functionalized with a ligand such as, but notlimited to, a silane having one or more hydrolyzable groups or afunctional or non-functional bipodal silane. In another such embodiment,the outer surface of the insulator layer is ligand-functionalized with aligand such as, but not limited to, mono-, di-, or tri-alkoxysilaneswith three, two or one inert or organofunctional substituents of thegeneral formula (R¹O)₃SiR²; (R¹O)₂SiR²R³; (R¹O) SiR²R³R⁴, where R¹ ismethyl, ethyl, propyl, isopropyl, or butyl, R², R³ and R⁴ are identicalor different and are H substituents, alkyls, alkenes, alkynes, aryls,halogeno-derivates, alcohols, (mono, di, tri, poly) ethyleneglycols,(secondary, tertiary, quaternary) amines, diamines, polyamines, azides,isocyanates, acrylates, methacrylates, epoxies, ethers, aldehydes,carboxylates, esters, anhydrides, phosphates, phosphines, mercaptos,thiols, sulfonates, and are linear or cyclic, a silane with the generalstructure (R¹O)₃Si—(CH₂)_(n)—R—(CH₂)_(n)—Si(RO)₃ where R and R¹ is H oran organic substituent selected from the group consisting of alkyls,alkenes, alkynes, aryls, halogeno-derivates, alcohols, (mono, di, tri,poly) ethyleneglycols, (secondary, tertiary, quaternary) amines,diamines, polyamines, azides, isocyanates, acrylates, methacrylates,epoxies, ethers, aldehydes, carboxylates, esters, anhydrides,phosphates, phosphines, mercaptos, thiols, sulfonates, and are linear orcyclic, a chlorosilane, or an azasilane. In another such embodiment, theouter surface of the insulator layer is ligand-functionalized with aligand such as, but not limited to, organic or inorganic compounds withfunctionality for bonding to a silica surface by chemical ornon-chemical interactions such as but not limited to covalent, ionic,H-bonding, or Van der Waals forces. In yet another such embodiment, theouter surface of the insulator layer is ligand-functionalized with aligand such as, but not limited to, the methoxy and ethoxy silanes(MeO)₃SiAllyl, (MeO)₃SiVinyl, (MeO)₂SiMeVinyl, (EtO)₃SiVinyl,EtOSi(Vinyl)₃, mono-methoxy silanes, chloro-silanes, or1,2-bis-(triethoxysilyl)ethane. In any case, in an embodiment, the outersurface of the insulator layer is ligand-functionalized to impartsolubility, dispersability, heat stability, photo-stability, or acombination thereof, to the semiconductor structure. For example, in oneembodiment, the outer surface of the insulator layer includes OH groupssuitable for reaction with an intermediate linker to link smallmolecules, oligomers, polymers or macromolecules to the outer surface ofthe insulator layer, the intermediate linker one such as, but notlimited to, an epoxide, a carbonyldiimidazole, a cyanuric chloride, oran isocyanate.

With reference again to the above described coated nanocrystalline coreand nanocrystalline shell pairings, in an embodiment, thenanocrystalline core has a diameter approximately in the range of 2-5nanometers. The nanocrystalline shell has a long axis and a short axis,the long axis having a length approximately in the range of 5-40nanometers, and the short axis having a length approximately in therange of 1-5 nanometers greater than the diameter of the nanocrystallinecore. The insulator layer has a thickness approximately in the range of1-20 nanometers along an axis co-axial with the long axis and has athickness approximately in the range of 3-30 nanometers along an axisco-axial with the short axis.

A lighting apparatus may include a light emitting diode and a pluralityof semiconductor structures which, e.g., act to down convert lightabsorbed from the light emitting diode. For example, in one embodiment,each semiconductor structure includes a quantum dot having ananocrystalline core composed of a first semiconductor material and ananocrystalline shell composed of a second, different, semiconductormaterial at least partially surrounding the nanocrystalline core. Eachquantum dot has a photoluminescence quantum yield (PLQY) of at least90%. An insulator layer encapsulates each quantum dot.

As described briefly above, an insulator layer may be formed toencapsulate a nanocrystalline shell and anisotropic nanocrystallinecore. For example, in an embodiment, a layer of silica is formed using areverse micelle sol-gel reaction. In one such embodiment, using thereverse micelle sol-gel reaction includes dissolving the nanocrystallineshell/nanocrystalline core pairing in a first non-polar solvent to forma first solution. Subsequently, the first solution is added along with aspecies such as, but not limited to, 3-aminopropyltrimethoxysilane(APTMS), 3-mercapto-trimethoxysilane, or a silane comprising aphosphonic acid or carboxylic acid functional group, to a secondsolution having a surfactant dissolved in a second non-polar solvent.Subsequently, ammonium hydroxide and tetraorthosilicate (TEOS) are addedto the second solution.

Thus, semiconductor nanocrystals coated with silica according to theinvention may be made by a sol-gel reaction such as a reverse micellemethod. As an example, FIG. 7 illustrates operations in a reversemicelle approach to coating a semiconductor structure, in accordancewith an embodiment of the invention. Referring to part A of FIG. 7, aquantum dot heterostructure (QDH) 702 (e.g., a nanocrystallinecore/shell pairing) has attached thereto a plurality of TOPO ligands704, TOP ligands 706, and Oleic Acid 705. Referring to part B, theplurality of TOPO ligands 704, TOP ligands 706, and Oleic Acid 705 areexchanged with a plurality of Si(OCH₃)₃(CH₂)₃NH₂ ligands 708. Thestructure of part B is then reacted with TEOS (Si(OEt)₄) and ammoniumhydroxide (NH₄OH) to form a silica coating 710 surrounding the QDH 702,as depicted in part C of FIG. 7. FIG. 8 is a transmission electronmicroscope (TEM) image 800 of silica coated 802 CdSe/CdS core/shellquantum dots 804 having complete silica encapsulation, in accordancewith an embodiment of the invention. Thus, a reverse micelle is formedafter adding ammonium hydroxide and tetraethylorthosilicate (TEOS), thesource for the silica coating. TEOS diffuses through the micelle and ishydrolyzed by ammonia to form a uniform SiO₂ shell on the surface of thequantum dot. This approach may offer great flexibility to incorporatequantum dots of different sizes. In one such embodiment, the thicknessof the insulator layer formed depends on the amount of TEOS added to thesecond solution.

With reference again to the above described method of forming coatednanocrystalline core and nanocrystalline shell pairings, in anembodiment, the first and second non-polar solvents are cyclohexane. Inan embodiment, forming the coating layer includes forming a layer ofsilica and further includes using a combination of dioctyl sodiumsulfosuccinate (AOT) and tetraorthosilicate (TEOS). In anotherembodiment, however, forming the layer includes forming a layer ofsilica and further includes using a combination of polyoxyethylene (5)nonylphenylether and tetraorthosilicate (TEOS). In another embodiment,however, forming the layer includes forming a layer of silica andfurther includes using cationic surfactants such as CTAB(cetyltrimethylammonium bromide), anionic surfactants, non-ionicsurfactants, or pluronic surfactants such as Pluronic F 127 (an ethyleneoxide/propylene oxide block co-polymer) as well as mixtures ofsurfactants.

Upon initiation of growth of a silica shell, the final size of thatshell may be directly related to the amount of TEOS in the reactionsolution. Silica coatings according to embodiments of the invention maybe conformal to the core/shell QDH or non-conformal. A silica coatingmay be between about 3 nm and 30 nm thick. The silica coating thicknessalong the c-axis may be as small as about 1 nm or as large as about 20nm. The silica coating thickness along the a-axis may be between about 3nm and 30 nm. Once silica shelling is complete, the product is washedwith solvent to remove any remaining ligands. The silica coated quantumdots can then be incorporated into a polymer matrix or undergo furthersurface functionalization. However, silica shells according toembodiments of the invention may also be functionalized with ligands toimpart solubility, dispersability, heat stability and photo-stability inthe matrix.

In another aspect, quantum dot composite compositions are described. Forexample, the quantum dots (including coated quantum dots) describedabove may be embedded in a matrix material to make a composite using aplastic or other material as the matrix. In an embodiment, compositecompositions including matrix materials and silica coated core/shellquantum dots having photoluminescence quantum yields between 90 and 100%are formed. Such quantum dots may be incorporated into a matrix materialsuitable for down converting in LED applications.

Composites formed by conventional approaches typically suffer fromnon-uniform dispersion of quantum dots throughout the matrix materialwhich can result in particle agglomeration. Agglomeration may be sosevere as to result in emission quenching reducing light output. Anotherproblem is lack of compatibility between the quantum dots and the matrixreduces composite performance. Lack of materials compatibility mayintroduce a discontinuity at the polymer/quantum dot interface wherecomposite failure may initiate when it is deployed in ordinary use.

Accordingly, there remains a need for a composite material having aquantum dot composition in a matrix that is strong, resistant to thermaldegradation, resistant to chemical degradation, provides good adhesionbetween the coated quantum dot and coupling agent and provides goodadhesion between the coupling agent and the polymer matrix. Embodimentsdescribed below include quantum dots incorporated into compositematrixes to produce high refractive index films having a high PLQYsuitable for solid state device lighting including light emittingdiodes.

In an embodiment, an approach for incorporating quantum dots into matrixmaterials includes coating the quantum dot with a silica shell andreacting the silica shell with a silane coupling agent having tworeactive functionalities under the proper conditions. Such anarrangement drives a condensation reaction, binding one end of thesilane to the silica surface and leaving the other end of the moleculeexposed for integration into a matrix. Other approaches include using acurable material such as metal oxide nanocrystals in a matrix material.In the curable material, metal oxide nanocrystals are linked to apolymer matrix via titanate or a zirconate coupling agents as well as asilane coupling agent, where the metal atoms of the coupling agent linkto the oxygen atoms of the metal oxide nanocrystals. Since metal oxidesgenerally do not have a higher refractive index, the curable materialincorporating the metal oxide nanocrystals typically can not achieve arefractive index sufficient to improve the light extraction efficiencyof photons emitted by an LED in a solid-state device. A high refractiveindex material including zinc sulfide (ZnS) in a matrix material isanother approach attempted. In making the high refractive indexmaterial, ZnS colloids are synthesized with ligands having hydroxylfunctional groups that are linked to isocyanate function groups presenton an oligomer backbone in the matrix material.

In a general embodiment, a composite includes a matrix material. Aplurality of semiconductor structures (e.g., quantum dot structureshaving a coated or non-coated core/shell pairing, such as the structuresdescribed above) is embedded in the matrix material. In an embodiment, alighting apparatus includes a light emitting diode and a compositecoating the light emitting diode. The composite may be formed byembedding quantum dots in a matrix material described below.

With reference to the above described composite, in an embodiment, eachof the plurality of semiconductor structures is cross-linked with,polarity bound by, or tethered to the matrix material. In an embodiment,each of the plurality of semiconductor structures is bound to the matrixmaterial by a covalent, dative, or ionic bond. By way of example, FIGS.9A-9C illustrate schematic representations of possible compositecompositions for quantum dot integration, in accordance with anembodiment of the invention. Referring to FIG. 9A, a nanocrystallinecore 902A and shell 904A pairing is incorporated into a polymer matrix906A by active cross-linking through multiple and interchain binding toform a cross-linked composition 908A. Referring to FIG. 9B, ananocrystalline core 902B and shell 904B pairing is incorporated into apolymer matrix 906B by polarity-based chemical similarity anddissolution to form a polarity based composition 908B. Referring to FIG.9C, a nanocrystalline core 902C and shell 904C pairing is incorporatedinto a polymer matrix 906C by reactive tethering by sparse binding andchemical similarity to form a reactive tethering based composition 908C.

With reference again to the above described composite, in an embodiment,one or more of the semiconductor structures further includes a couplingagent covalently bonded to an outer surface of the insulator layer. Forexample, in one such embodiment, the insulator layer includes or is alayer of silica (SiO_(x)), and the coupling agent is a silane couplingagent, e.g., having the formula X_(n)SiY_(4-n), where X is a functionalgroup capable of bonding with the matrix material and is one such as,but not limited to, hydroxyl, alkoxy, isocyanate, carboxyl, epoxy,amine, urea, vinyl, amide, aminoplast and silane, Y is a functionalgroup such as, but not limited to, hydroxyl, phenoxy, alkoxy, hydroxylether, silane or aminoplast, and n is 1, 2 or 3. In another embodiment,however, the coupling agent is one such as, but not limited to, atitanate coupling agent or a zirconate coupling agent. It is to beunderstood that the terms capping agent, capping ligand, ligand andcoupling agent may be used interchangeably as described above and,generally, may include an atom, molecule or other chemical entity ormoiety attached to or capable of being attached to a nanoparticle.Attachment may be by dative bonding, covalent bonding, ionic bonding,Van der Waals forces or other force or bond.

In the case that a silica surface of a silica coated quantum dot ismodified using silane coupling agents having multiple functionalmoieties, coupling to the surface of the silica shell and coupling to amatrix material and/or other matrix additives may be enabled. Such anapproach provides dispersed uniformly throughout the composite matrixusing as little effort (e.g., reaction energy) as possible. Strongerphysical and/or chemical bonding between the silica coated quantum dotsand the matrix resin occurs. Also, the silane coupling composition mustbe compatible with both the silica coated quantum dot, which isinorganic, and the polymer matrix, which may be organic. Without beingbound by any particular theory or principle, it is believed that thesilane coupling agent forms a bridge between the silica and the matrixresin when reactive functional groups on the silane coupling agentinteract with functional groups on the surface of the silica and/or thematrix resin. Because the functional groups involved are typically polarin nature, the coupling agent tends to be hydrophilic and readilydispersed in an aqueous size composition.

Matrix materials suitable for embodiments of the invention may satisfythe following criteria: they may be optically clear having transmissionin the 400-700 nm range of greater than 90%, as measured in a UV-Visspectrometer. They may have a high refractive index between about 1.0and 2.0, preferably above 1.4 in the 400-700 nm range. They may havegood adhesion to an LED surface if required and/or are sufficientlyrigid for self-supporting applications. They may able to maintain theirproperties over a large temperature range, for example −40° C. to 150°C. and over a long period of time (over 50,000 hours at a lightintensity typically 1-10 w/cm2 of 450 nm blue light).

Thus, with reference again to the above described composite, in anembodiment, the insulator layer is composed of a layer of silica(SiO_(x)), and the matrix material is composed of a siloxane copolymer.In another embodiment, the matrix material has a UV-Vis spectroscopytransmission of greater than 90% for light in the range of 400-700nanometers. In an embodiment, the matrix material has a refractive indexapproximately in the range of 1-2 for light in the range of 400-700nanometers. In an embodiment, the matrix material is thermally stable ina temperature range of −40-250 degrees Celsius. In an embodiment, thematrix material is composed of a polymer such as, but not limited to,polypropylene, polyethylene, polyesters, polyacetals, polyamides,polyacrylamides, polyimides, polyethers, polyvinylethers, polystyrenes,polyoxides, polycarbonates, polysiloxanes, polysulfones, polyanhydrides,polyamines, epoxies, polyacrylics, polyvinylesters, polyurethane, maleicresins, urea resins, melamine resins, phenol resins, furan resins,polymer blends, polymer alloys, or mixtures thereof. In one suchembodiment, the matrix material is composed of a polysiloxane such as,but not limited to, polydimethylsiloxane (PDMS),polymethylphenylsiloxane, polydiphenylsiloxane and polydiethylsiloxane.In an embodiment, the matrix material is composed of a siloxane such as,but not limited to, dimethylsiloxane or methylhydrogen siloxane.

Additionally, with reference again to the above described composite, inan embodiment, the plurality of semiconductor structures is embeddedhomogeneously in the matrix material. In an embodiment, the compositefurther includes a compounding agent embedded in the matrix material.The compounding agent is one such as, but not limited to, anantioxidant, a pigment, a dye, an antistatic agent, a filler, a flameretardant, an ultra-violet (UV) stabilizer, or an impact modifier. Inanother embodiment, the composite further includes a catalyst embeddedin the matrix material, the catalyst one such as, but not limited to, athiol catalyst or a platinum (Pt) catalyst.

Accordingly, in an embodiment, a method of fabrication includes forminga plurality of semiconductor structures embedded the semiconductorstructures in a matrix material (or embedding preformed semiconductorstructures in a matrix material). In one such embodiment, embedding theplurality of semiconductor structures in the matrix material includescross-linking, reactive tethering, or ionic bonding the plurality ofsemiconductor structures with the matrix material. In an embodiment, themethod further includes surface-functionalizing an insulator layer forthe semiconductor structures prior to embedding the plurality ofsemiconductor structures in the matrix material. In one such embodiment,the surface-functionalizing includes treating the insulator layer with asilane coupling agent. However, in an alternative embodiment, coatedsemiconductor structures are embedded in a matrix by using a ligand-freeinsulator layer.

In another embodiment, simple substitution at the surface of the silicacoated quantum dots is effective for stable integration withoutundesired additional viscosity and is suitable to produce alow-viscosity product such as a silicone gel. In one embodiment of theinvention a composite incorporates quantum dots which crosslink with thematrix through silane groups and which possess an adequate number ofsilane groups in order to form an elastic network. In addition, adequateadhesion to various substrates is enabled. Furthermore, silicone-basedmatrixes may be used. A structure of such polymers may be obtained whichform microstructures in the crosslinked composition, thereby yieldingcross-linked polymer compounds with an excellent mechanical strength.Furthermore, because of the distribution of the reactive silane groups,a high elasticity may be obtained after cross-linking.

In another aspect, alloyed nanocrystals may be incorporated asnanocrystalline cores for quantum dots based on heterostructures.Although embodiments described herein are not so limited, examples beloware directed toward synthesis of alloyed ternary CdSe_(n)S_(n-1)nanocrystals.

To provide context, a seeded semiconductor quantum rod architecture maybe employed to optimize quantum dot absorption and photoluminescencecharacteristics for the purposes of downconverting blue light,particularly for solid-state lighting applications. The architectureutilizes a Type I electronic structure created by the combination of thesemiconductor seed material as the core and semiconductor rod materialas the shell, resulting in an absorption that is dominated by the rodmaterial. Furthermore, the result is an emission peak which is dictatedby the seed material and size/shape, but which is also affected by thediameter and length of the rod. An example of such an architecture whichemits between 600 and 620 nm is a seed which is approximately 4nanometers in diameter (minor axis) coated with at least one othermaterial which results in an overall particle that is rod shaped,approximately 6-7 nanometers in diameter, and approximately 20-25nanometers in length.

To provide further context, emitters such as those described above maybe optimized to exhibit very high photoluminescence at both roomtemperature and high temperature in a matrix. Additionally, veryreliable performance may be achieved under a variety of stressconditions. In order to shift the emission peak of this exemplaryparticle to a higher energy, for example between 500 and 560 nanometersor even higher (e.g., less than approximately 500 nanometers), using thesame seeded rod architecture, the seed size must become smaller. Inaccordance with one or more embodiments, experiments have been carriedout with seeds as small as 2 nanometers (minor axis). However, aftercoating with a material to form a rod in accordance with an establishedbaseline process as well as modifications of that process, the centroidemission peak is consistently at least 560 nm or higher, as shown inFIG. 13.

FIG. 13 is a plot 1300 of CdSe seed QD band edge absorption versus(CdSe)CdS (QD)QR centroid emission, in accordance with an embodiment ofthe invention. Referring to plot 1300, band edge absorption of pure CdSeseeds shows that in cases where the band edge absorption is as low as430 nanometers, the result is an emission peak at 580 nanometers.Furthermore, regardless of band edge absorption, emission remainsconsistently above 560 nanometers.

Thus, even though the seed is much smaller than 4 nanometers, theaddition of the rod material shifts the emission peak substantiallyredder than the desired value. In addition, changing the size of theseed means that the overall dimensions of the rod change, sometimesdrastically, which in turn means that other subsequent fabricationoperations may need to be re-optimized each time the seed size ischanged.

Addressing one or more of the above observations, in accordance with oneor more embodiments herein, an alternative to altering seed size fortuning the emission of a seeded rod emitter architecture is provided.More particularly, instead of changing seed size, the seed compositionis changed by alloying either the entire seed (in one embodiment) orsome portion of the seed (in another embodiment) with a higher bandgapmaterial. In either case, the general approach can be referred to as analloying of the seed or nanocrystalline core portion of aheterostructure quantum dot. By alloying the seed or nanocrystallinecore, the bandgap can be changed without changing the size of the seedor core. As such, the emission of the seed or core can be changedwithout changing the size of the seed or core. In one such embodiment,the size of the seed is fixed at the optimum size of a red-emittingseed, or roughly 4 nanometers. The fixed sized means that the size ofthe rod and the subsequent synthetic operations may not need to besubstantially re-optimized or altered as the emission target of thequantum dots is changed. The concept is described in association withFIGS. 14A and 14B.

FIG. 14A is a schematic 1400A illustrating emission wavelength (nm)decrease as a function of energy increase, in accordance with anembodiment of the invention. The schematic 1400A shows a same size seedor nanocrystalline core 1402 within a rod or nanocrystalline shell 1404,neither of which changes size. Instead, emission shifts (e.g.,wavelength decrease, energy increase) as the extent of seed 1402alloying is modified along the arrow shown in FIG. 14A. In one suchembodiment, the % of alloy represents an amount of a secondary seedmaterial makes up the total core material.

For comparison, FIG. 14B is a schematic 1400B illustrating emissionwavelength (nm) decrease as a function of energy increase, in accordancewith another embodiment of the invention. The schematic 1400B shows aseed or nanocrystalline core 1452 that is reduced in size within a rodor nanocrystalline shell 1454 that is also reduced in size. Emissionshifts (e.g., wavelength decrease, energy increase) as the extent ofseed size is reduced along the arrow shown in FIG. 14B. The compositionof the seed or core 1452, however, is not changed in this case.

Accordingly, in one or more embodiments described herein, optimumphysical dimensions of a seeded rod are maintained as constant whiletuning the emission peak of the heterostructure quantum dot. This can beperformed without changing the dimensions of the seed (and therefore therod) for each emission color. In a particular embodiment, a quantum dotincludes an alloyed Group II-VI nanocrystalline core. The quantum dotalso includes a Group II-VI nanocrystalline shell composed of asemiconductor material composition different from the alloyed GroupII-VI nanocrystalline core. The Group II-VI nanocrystalline shell isbonded to and completely surrounds the alloyed Group II-VInanocrystalline core. In one such embodiment, the alloyed Group II-VInanocrystalline core is composed of CdSe_(n)S_(1-n) (0<n<1), and theGroup II-VI nanocrystalline shell is composed of CdS. In a specificembodiment, the alloyed Group II-VI nanocrystalline core has a shortestdiameter of greater than approximately 2 nanometers, and the quantum dothas an exciton peak less than 555 nanometers. In a particularembodiment, the alloyed Group II-VI nanocrystalline core has a shortestdiameter of approximately 4 nanometers, and the quantum dot has anexciton peak less than 555 nanometers, as is described in greater detailbelow

Perhaps more generally, in an embodiment, a quantum dot includes aternary semiconductor nanocrystalline core. The quantum dot alsoincludes a binary semiconductor nanocrystalline shell including two ofthree elements of the ternary semiconductor nanocrystalline core. Thebinary semiconductor nanocrystalline shell is bonded to and completelysurrounds the ternary semiconductor nanocrystalline core. In one suchembodiment, the ternary semiconductor nanocrystalline core is composedof a first Group II-VI material, and the binary semiconductornanocrystalline shell is composed of a second, different, Group II-VImaterial. In one such embodiment, the first Group II-VI material isCdSe_(n)S_(1-n) (0<n<1), and the second Group II-VI material is CdS.

The terms “binary” and “ternary” as used herein refer to compoundsemiconductor materials composed of two or three elements, respectively.For example, CdS is a binary semiconductor material since it is composedof Cd and S. On the other hand, CdSe_(n)S_(1-n) (0<n<1) is a ternarysemiconductor material since it is composed of Cd, Se and S. In the casethat the binary semiconductor nanocrystalline shell includes two of thethree elements of the ternary semiconductor nanocrystalline core, in anexemplary embodiment, a CdS binary semiconductor nanocrystalline shellincludes Cd and S which are also included in a CdSe_(n)S_(1-n) (0<n<1)ternary semiconductor nanocrystalline core.

Regarding actual synthesis of such alloyed seeds or cores, orhetereostructures having such seeds or cores therein, Example 17,provided below under Exemplary Synthetic Procedures, outlines anexemplary synthesis of ternary CdSe_(n)S_(n-1) QD seeds, in accordancewith an embodiment of the invention. Example 18, provided below underExemplary Synthetic Procedures, outlines an exemplary synthesis of highquality ternary CdSe_(n)S_(n-1) QD seeds for use in high performancenano-sized, semiconducting heterostructures, in accordance with anembodiment of the invention. Example 19, provided below under ExemplarySynthetic Procedures, outlines an exemplary synthesis of high qualityternary CdSe_(n)S_(n-1) QD seeds for use in high performance nano-sized,semiconducting heterostructures where the synthesis involves the use ofsulfur in allylamine, in accordance with an embodiment of the invention.Example 20, provided below under Exemplary Synthetic Procedures,outlines an exemplary synthesis of high quality ternary CdSe_(n)S_(n-1)QD seeds for use in high performance nano-sized, semiconductingheterostructures where the synthesis involves the use of sulfur inoctadecene, in accordance with an embodiment of the invention.

In one aspect, so-called blue alloyed cores may be fabricated. FIG. 15includes a UV-Vis spectrum 1500 of CdSeS QDs with λ_(max) atapproximately 464.7 nm and a UV-Vis spectrum 1502 of CdSeS QDs withλ_(max) at approximately 476.2 nm, in accordance with an embodiment ofthe invention. Referring to FIG. 15, the blue alloyed cores weresynthesized according to the procedure of Example 17.

FIG. 16 includes a transmission electron microscope (TEM) image 1600 anda TEM image 1602 comparing CdSe QDs and CdSeS QDs, respectively, inaccordance with an embodiment of the invention. Referring to FIG. 16,with the same exciton peak, the CdSeS QDs are clearly larger. That is,the exciton peak should otherwise be redder than 465 nanometers withoutthe presence of the Sulfur component.

FIG. 17 includes a TEM image 1700 and a TEM image 1702 comparing CdSeQDs and CdSeS QDs, respectively, in accordance with another embodimentof the invention. Referring to FIG. 17, the TEM comparison shows CdSeseeds with an exciton peak around 560 nanometers as compared with CdSeSseeds having an exciton peak at 465 nanometers.

FIG. 18 is a plot 1800 showing transmission spectroscopy curves foralloyed nanocrystals, in accordance with an embodiment of the invention.Referring to FIG. 18, the 4.2 nanometer CdSeS cores have a 510 nm 1stexciton peak. By comparison, a typical 4.2 nanometer CdSe has an excitonpeak around 555 nm. In one embodiment, then, an alloyed Group II-VInanocrystalline core has a shortest diameter of greater thanapproximately 2 nanometers, and the resulting quantum dot has an excitonpeak less than 555 nanometers. In a particular embodiment, the alloyedGroup II-VI nanocrystalline core has a shortest diameter ofapproximately 4 nanometers, and the resulting quantum dot has an excitonpeak less than 555 nanometers

Overall, then, in an embodiment, a method of tuning an exciton peak fora quantum dot involves selecting a composition and a sizing of analloyed Group II-VI nanocrystalline core corresponding to a targetedexciton peak for the quantum dot. The method also involves forming thealloyed Group II-VI nanocrystalline core having the composition and theparticular sizing. The method also involves forming a Group II-VInanocrystalline shell having a semiconductor material compositiondifferent from the alloyed Group II-VI nanocrystalline core, the GroupII-VI nanocrystalline shell bonded to and completely surrounding thealloyed Group II-VI nanocrystalline core.

It is to be appreciated that other aspects of quantum dot formation(e.g., insulator coating formation) and quantum dot application (e.g.,LED application) can be applied to the above described alloyedseed/nanocrystalline cores.

As previously discussed herein, a seeded semiconductor quantum rodarchitecture may be employed to optimize quantum dot absorption andphotoluminescence characteristics for the purposes of downconvertingblue light, particularly for solid-state lighting applications. Thearchitecture utilizes a Type I electronic structure created by thecombination of the semiconductor seed material and semiconductor rodmaterial, resulting in an absorption which is dominated by the rodmaterial. Furthermore, the result is an emission peak which is dictatedby the seed material and size/shape, but which is also affected by thediameter and length of the rod.

In one embodiment, materials used to create the rod-shaped shell portionof the quantum dot heterostructure are able to absorb blue light (e.g.,450 nm), while transferring the excited state in the Type I electronicstructure to the seed or core, which emits at a lower energy. Becausethe seed required to emit green light (520 to 570 nm) has a largebandgap, the bandgap can potentially be close to that of CdS, which, asdiscussed above, is a binary semiconductor nanocrystalline materialtypically used to grow a Group II-VI rod. For example, FIG. 19 depictsvarious quantum dot structures 1900 using a binary semiconductornanocrystalline core and a binary semiconductor nanocrystalline shellbonded to and surrounding the binary semiconductor nanocrystalline core.The binary semiconductor nanocrystalline core is composed of a firstGroup II-VI material, and the binary semiconductor nanocrystalline shellis composed of a second, different, Group II-VI material. In one suchembodiment, the first Group II-VI material is CdSe_(n)S_(1-n) (0<n<1),and the second Group II-VI material is CdS. The semiconductor structurefurther includes a nanocrystalline outer shell at least partiallysurrounding the nanocrystalline shell and, in one embodiment, thenanocrystalline outer shell completely surrounds the nanocrystallineshell. The nanocrystalline outer shell is composed of a thirdsemiconductor material different from the semiconductor material of theshell and different from the semiconductor material of the core. In onesuch embodiment, the material is ZnS. In a particular such embodiment,the first semiconductor material is cadmium selenide (CdSe) or cadmiumselenide sulfide (CDSeS), the second semiconductor material is cadmiumzinc sulfide (CdZnS), and the third semiconductor material is zincsulfide (ZnS). Using binary semiconductor materials, the transitionbetween Type I and Type II electronic heterostructure overlap occursaround 594 nm (using bulk bandgaps for the shell layers).

In contrast to a CdS rod, a ZnS rod exhibits a large degree of Type Iheterostructure confinement, but ZnS does not absorb blue light (450nm). Therefore, one embodiment of the invention incorporates Zn into aCdS rod to adjust the bandgap sufficiently to confine the seed withoutdecreasing the absorbance at 450 nm. In one embodiment, the amount of Znincorporated in a CdS rod is approximate 20%. FIG. 20 depicts variousquantum dot structures 2000, according to embodiments of the invention,that use a ternary semiconductor nanocrystalline core and a ternarysemiconductor nanocrystalline shell bonded to and surrounding theternary semiconductor nanocrystalline core. The ternary semiconductornanocrystalline core is composed of a first Group II-VI material, andthe ternary semiconductor nanocrystalline shell is composed of a second,different, Group II-VI material. In one such embodiment, the first GroupII-VI material is CdSe_(n)S_(1-n) (0<n<1), and the second Group II-VImaterial is CdZnS. The semiconductor structure further includes ananocrystalline outer shell at least partially surrounding thenanocrystalline shell. The nanocrystalline outer shell is composed of athird semiconductor material different from the semiconductor materialof the shell and different from the semiconductor material of the core.In one such embodiment, the material is ZnS. Using ternary semiconductormaterials, the transition between Type I and Type II heterostructureoverlap is delayed until approximately 490 nm (using bulk bandgap forthe outer shell layer).

With reference to FIG. 21, embodiments of the invention provide for avery stable, high performance doped/alloyed semiconductor nanorodstructure 2100A, 2100B, composed of a quantum dot seed, and a ternarysemiconductor nanocrystalline shell 2115 (e.g., CdZnS, or CdMgS). In oneembodiment 2100A, the seed is a binary semiconductor nanocrystallinecore 2105 (e.g., CdSe). In another embodiment 2100B, the seed is analloyed, ternary semiconductor nanocrystalline core 2110 (e.g., CdSeS).According to one embodiment, the seeds must have a very small diameterand/or exhibit a high energy first exciton peak, usually greater (bluer)than 460 nm. In both embodiments, the resulting structures exhibit highPLQY emission at <550 nm. In contrast, a quantum dot with a binarysemiconductor nanocrystalline core and a binary semiconductornanocrystalline shell may yield emission at <550 nm but only with a muchsmaller particle, which is less stable and has a lower PLQY.

In one embodiment, the seeded rods 2100A, 2100B have a ternarysemiconductor nanocrystalline shell with a short axis having a length inthe range of 5-8 nanometers, and a long axis having a lengthapproximately in the range of 16-30 nanometers.

FIG. 22 includes a transmission electron microscope (TEM) image 2200 anda TEM image 2202, respectively, of a ternary CdZnS shell on a binaryCdSe core with total length of 17.1 nm and total width of 4.0 nm, and aternary CdZnS shell on a ternary CdSeS core with total length of 20.0 nmand total width of 4.2 nm. With the combination of a binary or ternarycore and a ternary alloyed CdZnS shell, “green” emission wavelengths inthe range of 530-540 nm are achieved, while maintaining high PLQY (up to99%), and a Type I or quasi-Type II electronic structure, as depicted inFIG. 20. Furthermore, all this is achieved while still maintainingreliable and stable morphology of a seeded rod of standard dimensions of16-20 nm (average length) by 4-6 nm (average width).

Material analyses of the seeded rods by energy dispersive X-rayanalytical system (SEM-EDX) and inductively coupled plasma opticalemission spectroscopy (ICP-OES) corroborate alloying of metals into thesemiconductor nanocrystalline shell. The advantage of doping/alloying isevident in the ability to tune the wavelength of emission whilemaintaining high photoluminescence quantum yield with a high degree ofrobustness.

As previously discussed herein, embodiments of the invention employ aseeded semiconductor quantum rod architecture to optimize quantum dotabsorption and photoluminescence characteristics. Such embodiments maybe used for purposes of downconverting blue light, particularly forsolid-state lighting applications, as described, for example, by theassignee of U.S. patent application Ser. Nos. 13/485,756, 13/485,761,and 13/485,762, the contents of which are incorporated herein byreference. In particular, by using a different core and shell materials,embodiments of the invention create a quantum dot heterostructurematerial. The semiconductor bandgaps of these materials are important,but also important is the relative alignment of the electronic energylevels of the materials. Specifically, avoiding a Type II bandgapheterojunction (as depicted at 2300 in FIG. 23) is important forrealizing high brightness quantum dots. Quantum dot architectureaccording to embodiments of the invention utilizes a Type I electronicstructure created by the combination of the semiconductor seed materialas the core and semiconductor rod material as the shell, resulting in anabsorption which is dominated, that is, substantially controlled, by therod material, and an emission peak which is dictated, that is,substantially controlled, by the seed material and size, and alsoaffected by the diameter and length of the rod material. An example ofthis architecture, which emits between 600 and 620 nm, is a seed that is4 nm in diameter (minor axis) and coated with at least one othermaterial, which results in an overall particle that is rod shaped, 6-7nm in diameter, and 20-25 nm in length. This emitter is optimized toexhibit very high photoluminescence at both room temperature and hightemperature in a matrix, as well as very reliable performance under avariety of stress conditions.

Materials used to manufacture the rod in a second step and/or for theadditional semiconductor barrier coating or outer shell layer in a thirdstep of the architecture make use of successively wider bandgapmaterials, according to an embodiment. Furthermore, the band alignmentof the shell layer and outer shell layer should preferentially promotethe localization of the wave function of both the electron and the holeto the core portion where radiative recombination can occur.Additionally, minimal lattice constants mismatch is very desirable toreduce strain during growth between adjacent materials. In the priorart, CdS, ZnSe, and ZnS are commonly used to coat CdSe, and ZnSe and ZnShave been used to coat CdS to create quantum dot heterostructures withType I or quasi Type II heterojunction bandgap alignments. Inembodiments of the invention, however, wide-bandgap magnesium-basedsemiconductor materials are employed in the second layer (the rodmaterial) and/or third layer (the outer shell) of the quantum dotheterostructure. In one embodiment, a wide bandgap is greater than 2 eV.In particular, magnesium chalcogenides, such as MgO, MgS, and MgSe, arematerials with wide bandgaps that have suitable band alignments withminimal lattice constants mismatch for adjacent materials used in theseeded rod quantum dot configuration. In addition to binary magnesiumchalcogenides, magnesium can be incorporated and alloyed with othersemiconductor materials such as CdS, ZnSe, and ZnS to create ternarysemiconductor materials. These ternary alloyed semiconductor materialsmay be engineered to have a more optimal bandgap, band alignment, andlattice mismatch to realize a structure with a Type I band alignment.Furthermore, such alloying of Mg allows for facile incorporation ofnovel semiconductor quantum dot architectures into existing syntheticprocesses. This is particularly useful when designing and maintaining aType I architecture while using wider bandgap, bluer core materials inthe quantum dot structure, such as with small binary CdSe or ternaryCdSe_(m)S_(m-1) seed, or core, materials.

Embodiments of the invention allow bandgap engineering via theincorporation of Magnesium in a given quantum dot electronic structurein order to maintain a Type I alignment architecture with higher quantumefficiencies when employing wider bandgap (bluer) core materials.Maintaining blue emission from a quantum dot core while employing athick semiconductor shell (used for minimizing self-absorption andprotection from degradation) can be a challenge because the bandgap ofthe core is influenced by the thickness of the shell. By making anappropriate alloy of CdZnS, both of the desirable properties of Type Ibandgap alignment and a highly absorbing shell layer can be maintained.However, in order to add a third layer, an outer shell, which isprotective but not necessarily absorbing, the embodiments describedherein use an alloy of Zn_(m)Mg_(m-1)S. Similarly, instead of a CdZnSalloy for the seed or first shell layer, a Cd_(n)Mg_(n-1)S alloy can beemployed in other embodiments. The addition of Mg in the right ratiosallows for the careful tuning of the bandgap properties required foroptimal performance. In one embodiment, the ratio of Mg to Zn depends onthe bandgap of the seed or shell layer that it is being covered. Thebluer the core or core/shell combination, the more Mg needs to be usedrelative to Zn to maintain good Type I bandgap nesting.

As previously noted, in contrast to a CdS rod, a ZnS rod exhibits alarge degree of Type I heterostructure confinement, but ZnS does notabsorb blue light (450 nm). Therefore, one embodiment of the inventionincorporates Zn into a CdS rod to adjust the bandgap sufficiently toconfine the seed without decreasing the absorbance at 450 nm. In oneembodiment, the amount of Zn incorporated in a CdS rod is approximately20%. FIG. 24 depicts various quantum dot structures 2400, according toembodiments of the invention, which use a ternary semiconductornanocrystalline core and a ternary semiconductor nanocrystalline shellbonded to and surrounding the ternary semiconductor nanocrystallinecore. The ternary semiconductor nanocrystalline core is composed of afirst Group II-VI material, and the ternary semiconductornanocrystalline shell is composed of a second, different, Group II-VImaterial. In one such embodiment, the first Group II-VI material isCdSe_(m)S_(m-1), and the second Group II-VI material is CdZnS. Thesemiconductor structure further includes a nanocrystalline outer shellat least partially surrounding the nanocrystalline shell. Thenanocrystalline outer shell is composed of a third semiconductormaterial different from the semiconductor material of the shell anddifferent from the semiconductor material of the core. In one suchembodiment, the material is ZnMgS. Using ternary semiconductormaterials, the transition between Type I and Type II heterostructureoverlap is delayed until approximately 490 nm (using bulk bandgap forthe outer shell layer).

An exemplary synthesis of (CdSe_(m)S_(m-1))Cd_(n)Mg_(n-1)S quantum dots(seed)rod follows. Trioctylphosphine oxide (TOPO), octadecylphosphonicacid (ODPA), hexylphosphonic acid (HPA), cadmium oxide (CdO), andmagnesium(II) acetylacetonate (Mg(acac)₂) are added into a three-neckroundbottom flask with a thermocouple probe, air condenser, and rubberseptum. Under argon flow, the mixture is stirred and heated to 120° C.The vessel is evacuated and the mixture degassed for 75 minutes,followed by purging with argon gas. The temperature is increased to 280°C. and then held for 70 minutes in order to dissociate CdO andMg(acac)₂. The temperature is increased to 320° C., after whichtrioctylphosphine (TOP) is injected via syringe. The reaction solventtemperature is set to and equilibrated at 280° C. The temperature isthen set to 260° C., after which trioctylphosphine sulfide

(Trioctylphosphine-sulfide (TOPS), ˜7.4% wt. sulfur) and theCdSe_(m)S_(m-1) seeds are rapidly injected at 280° C. The temperatureset point is maintained at 260° C. for 90 minutes, and then the heatingmantle and glass wool are removed and the reaction vessel is cooled downby flowing compressed air on the outside of the glass while stirring.The resulting reaction product is processed by standard procedurescommon in the field. Alternatively, magnesium ethoxide, magnesiumthiolate, organometallic magnesium precursors such as dibutyl magnesium,and/or other appropriate magnesium precursors may be employed in thisprocedure by adding via syringe under argon in the beginning of theprocess or at a slower rate via syringe pump immediately after injectionof TOPS.

In accordance with an embodiment of the invention, binary or ternarycore/ternary shell quantum dots may be coated with silica and otherligands to provide a structure having a high PLQY. One embodimentexploits a sol-gel process which encapsulates each quantum dotindividually in a silica shell, resulting in a very stable high PLQYquantum dot particle. The coated quantum dots disclosed herein mayadvantageously possess a narrow size distribution for CdSe corestability over time (assessed by PLQY and scattering in solution).

In a general embodiment, a semiconductor structure includes ananocrystalline core composed of a first semiconductor material. Thesemiconductor structure also includes an alloyed nanocrystalline shellcomposed of a second, different, semiconductor material at leastpartially surrounding the nanocrystalline core. An insulator layerencapsulates, e.g., coats, the alloyed nanocrystalline shell andnanocrystalline core. Thus, coated semiconductor structures includecoated structures such as the quantum dots described above. For example,in an embodiment, the nanocrystalline core is anisotropic, e.g., havingan aspect ratio between, but not including, 1.0 and 2.0. In anotherexample, in an embodiment, the nanocrystalline core is anisotropic andis asymmetrically oriented within the alloyed nanocrystalline shell. Inan embodiment, the nanocrystalline core and the alloyed nanocrystallineshell form a quantum dot.

With reference to the above described coated nanocrystalline core andalloyed nanocrystalline shell pairings, in an embodiment, the insulatorlayer is bonded directly to the alloyed nanocrystalline shell. In onesuch embodiment, the insulator layer passivates an outermost surface ofthe alloyed nanocrystalline shell. In another embodiment, the insulatorlayer provides a barrier for the alloyed nanocrystalline shell andnanocrystalline core impermeable to an environment outside of theinsulator layer. In any case, the insulator layer may encapsulate only asingle nanocrystalline shell/nanocrystalline core pairing. In anembodiment, the semiconductor structure further includes ananocrystalline outer shell at least partially surrounding the alloyednanocrystalline shell, between the alloyed nanocrystalline shell and theinsulator layer. The nanocrystalline outer shell is composed of a thirdsemiconductor material different from the alloyed semiconductor materialof the shell and, possibly, different from the semiconductor material ofthe core.

With reference again to the above described coated nanocrystalline coreand alloyed nanocrystalline shell pairings, in an embodiment, theinsulator layer is composed of a layer of material such as, but notlimited to, silica (SiO_(x)), titanium oxide (TiO_(x)), zirconium oxide(ZrO_(x)), alumina (AlO_(x)), or hafnia (HfO_(x)). In one suchembodiment, the layer is a layer of silica having a thicknessapproximately in the range of 3-100 nanometers. In an embodiment, theinsulator layer is an amorphous layer.

Thus, according to an embodiment of the invention, by alloying a binarysemiconductor nanocrystalline shell (e.g., a CdS rod) with Zn to shiftthe bandgap “bluer” (e.g., greater than 460 nm), a type-IIheterostructure system is avoided while providing protection to thecore. Furthermore, this ternary semiconductor nanocrystalline shellconfiguration minimizes self-absorption by maintaining shell absorptionat blue wavelengths typically used for down-shifting LED excitation.Such embodiments may also be used to create green downshifters whichexhibit both high PLQY and high reliability.

An exemplary synthesis of such alloyed rods, in accordance with anembodiment of the invention, follows. To a reaction flask (typicallybetween 50 and 250 mL, but not excluding larger flask sizes), add thefollowing: a) magnetic stir bar; b) solvent (TOPO is preferred; otherhigh boiling solvents are also possible, such as octadecene; c) cadmiumprecursor (such as cadmium oxide, but can also include cadmium formate,cadmium acetate, cadmium nitrate, cadmium stearate, and other cadmiumprecursors); d) Ligand 1: Long-chain phosphonic acid (generally useoctadecylphosphonic acid, technical grade, 90%; other long chainphosphonic acids may work as well); e) Ligand 2: Short chain phosphonicacid (generally use hexylphosphonic acid, technical grade, 90%; othershort chain phosphonic acids may work as well).

Next, heat up the reaction flask contents to 120 C under flowing UHPinert gas—the solvent will melt/liquefy and disperse other solids around60 C—begin stirring at this point at 800 rpm and continue stirringthroughout reaction. Then, de-gas this mixture at 120 C for a given time(for example, between 30 and 90 minutes depending on the metalprecursors involved).

After refilling the reaction flask with inert gas, raise the temperatureof the mixture to 280 C and begin the dissociation step. This stepinvolves dissociation of metal precursors into metal-phosphonate forms.The temperature of dissociation is maintained for 70-80 minutes, until aclear, colorless solution is observed, then lower the temperature of thereaction flask to 80 C, and then let equilibrate back to 120 C.

Next, de-gas this mixture a second time at 120 C for a given time (forexample, between 30 and 90 minutes depending on the metal precursorsinvolved), then raise the temperature to 320 C and equilibrate for 15-20minutes followed by injection of a mixture of co-ordinating ligandstri-octylphosphine (TOP) and 1,2-hexanediol (HDO). It is possible to usea variety of different 1,2-diols, long-chain mono-alcohols, andglycerol.

Lower the temperature to 300 C and then rapidly inject a mixture of: a)QD cores (CdSe binary or CdSeS ternary seeds) and b) 7.4 wt % sulfur:TOPstock solution. Simultaneously start dripping diethylzinc in1-octadecene solution via a syringe pump. The rate of infusion may bevaried depending upon how much Zn is needed to be incorporated in theternary CdZnS shell. Allow growth to occur for 45-120 minutes (continuedstirring, UHP argon flow, temperature maintained at reaction temperatureof 300 C).

After a growth period, cool to room temperature (with continued stirringand continued UHP argon flow), and at temperature, T, <80 C, expose toair and inject solvent (toluene or cyclohexane); recover and stir underargon until reaction solution below 25 C.

Follow with 2× precipitation/centrifugation cycles using IPA and MeOH asantisolvents, and toluene as solvent to purify materials. The finalsolid product is then dissolved in organic solvent (toluene ispreferred; other solvents likely possible, such as hexane, cyclohexane).

The best practice involves the following ratios:

i) Zn:Cd: (2.5-4):1

ii) Ligand 1:Ligand 2: 2.3:1

iii) Total ligand:total metal: 1.05:1

iv) Sulfur:Metal: 4:1

EXEMPLARY SYNTHETIC PROCEDURES Example 1

Synthesis of CdSe core nanocrystals. 0.560 g (560 mg) of ODPA solid wasadded to a 3-neck 25 ml round-bottom flask and 6 g TOPO solid was addedto the flask. 0.120 g (120 mg) of CdO solid was added to the flask. Withthe flask sealed and the reagents inside (CdO, ODPA, TOPO), heat thereaction to 120° C. under flowing UHP Argon gas. When the reactionmixture becomes liquid, begin stirring at 800 RPM to completelydistribute the CdO and ODPA. When the temperature equilibrates at around120° C., begin degassing the reaction mixture: Standard degas is for 30minutes at as low a vacuum as the system can maintain, preferablybetween 10-30 torr. After the first degas, switch the reaction back toflowing UHP Argon gas. The temperature of the reaction was raised to280° C. to dissociate the CdO. Dissociation is accompanied by a loss ofthe typical red color for CdO. After dissociation of the CdO, cool thereaction to 120° C. for the 2nd degassing step. Preferably this step isdone slowly. In one embodiment this is done in increments of 40 degreesand allowed to equilibrate at each step. When the reaction mixture hascooled to about 120° C., begin the second degassing step. The seconddegassing is typically 1 hour at the lowest vacuum level possible. Afterthe second degassing, switch the reaction back to flowing UHP Argon.Heat the reaction mixture. Inject 3.0 g TOP into the reaction solutionas temperature increases above 280° C. Equilibrate the reaction solutionat 370° C. When the reaction is equilibrated at 370° C., inject 0.836 gof 14% Se:TOP stock solution into the solution. The reaction is rununtil the desired visible emission from the core is achieved. For CdSecores the time is usually between 0.5 and 10 minutes. To stop thereaction: while continuing to stir and flow UHP Argon through thereaction, rapidly cool the solution by blowing nitrogen on the outsideof the flask. When the reaction temperature is around 80° C., expose thereaction solution to air and inject approximately 6 mL of toluene.Precipitate the CdSe nanocrystals through the addition of 2-propanol(IPA) to the reaction solutions. Preferably the mixture should beapproximately 50/50 (by volume) reaction solution/IPA to achieve thedesired precipitation. Centrifuge for 5 minutes at 6000 RPM. Redissolvethe CdSe in as little toluene as possible solid (<2 mL). Precipitate theCdSe again using IPA. Centrifuge. Decant the supernatant liquid.Dissolve the CdSe solid in anhydrous toluene.

Example 2

Synthesis of CdSe/CdS core-shell nanocrystal heterostructures havingPLQY>90%. Transfer 0.290 g (290 mg) of ODPA into a round bottom flask.Transfer 0.080 g (80 mg) of hexylphosphonic acid (HPA) into the flask.Transfer 3 g TOPO into the flask. Transfer 0.090 g (90 mg) of CdO solidinto the reaction flask. With the flask sealed and the reagents inside(CdO, ODPA, TOPO, HPA), heat the reaction to 120° C. under flowing UHPArgon gas. When the reaction mixture becomes liquid, at about 60° C.,begin stirring at 800 RPM to completely distribute the CdO, ODPA, andHPA. When the temperature settles at 120° C., begin degassing thereaction mixture. After the degas step, switch the reaction back toflowing UHP Argon gas. Raise the temperature of the reaction to 280° C.to dissociate the CdO. Increase the temperature set-point of thereaction to 320° C. Inject 1.5 g TOP into the reaction solution astemperature increases above 280° C. When the reaction is equilibrated at320° C., inject a mixture of 1.447 g of 7.4% S:TOP stock solution and0.235 g concentration-adjusted CdSe seed stock into the reactionsolution. Immediately reduce the set point of the temperature controllerto 300° C. Allow the reaction to proceed for the requisite time tonecessary to produce the desired length and width of shell, yielding arod having an aspect ratio as between 1.5 and 10, more preferablybetween 3 and 6. Reaction temperature for shell growth is between 120°C. and 380° C., preferably between 260° C. and 320° C., more preferablybetween 290° C. and 300° C.

The reaction is monitored by testing a sample to determine theabsorbance at 400 nm and the at the CdSe exciton peak. Most preferablythe reaction is stopped when the absorbance at 400 nm divided by theabsorbance at the CdSe exciton peak is between about 25-30, but theinvention contemplates that the absorbance ratio may be between about 6and about 100, preferably between about 15-35. By “stopping the growth”it is meant that any method steps may be employed known in the art ifdesired and available to cease the growth of the shell. Some methodswill lead to quicker cessation of shell growth than others.

Absorbance measuring may be performed by UV-VIS spectroscopic analyticalmethod, such as a method including flow injection analysis forcontinuous monitoring of the reaction. In an embodiment, the reaction isstopped or arrested by removing a heating mantle and allowing thereaction vessel to cool. When the reaction temperature is aroundapproximately 80 degrees Celsius, the reaction solution is exposed toair and approximately 4-6 mL of toluene is injected. The quantum dotsare purified by transferring the reaction solution into four smallcentrifuge tubes, so that an equal volume is in each tube. The QDHproduct is precipitated through the addition of 2-propanol (IPA) to thereaction solutions. Following centrifuging, the supernatant liquid isdecanted. The QDH is redissolved in as little toluene as possible (e.g.,less than approximately 2 mL) and re-concentrated into one centrifugetube. The precipitation and centrifugation steps are repeated. The finalsolid product is then dissolved in approximately 2 g of toluene.

Example 3

Synthesis of CdSe/CdS quantum dot having an absorbance ratio between6-100. A quantum dot was fabricated according to Example 2 and having anabsorbance ratio between 6-100. FIG. 10 is a transmission electronmicroscope (TEM) image 1000 of a sample of core/shell (1002/1004)CdSe/CdS quantum dots, in accordance with an embodiment of theinvention. The TEM image 1000 indicates that there are substantially nostructural defects as can be deduced from the low density of stackingfaults and lack of other visible defects along the semiconductorstructure 1002/1004.

Example 4

Synthesis of CdSe/CdS red quantum dot with a PLQY=96% Quantum dots werefabricated according to Example 2 and having an absorbance ratio between6-100, and having a PLQY of 96% at 606 nm. The average length (from TEMdata) is 22.3 nm±3.1 nm. The average width (from TEM data) is 6.0 nm±0.6nm. The average aspect ratio (from TEM data) is 3.8±0.6. FIG. 11 is aplot 1100 including a UV-Vis absorbance spectrum 1102 andphotoluminescent emission spectrum 1104 for a CdSe/CdS core/shellquantum dot having a PLQY of 96%, in accordance with an embodiment ofthe invention. The quantum dot has essentially no overlapping absorptionand emission bands. FIG. 12 is a transmission electron microscope (TEM)image 1200 of a sample of CdSe/CdS quantum dots 1202 fabricatedaccording to example 4, in accordance with an embodiment of theinvention.

Example 5

Reactive Ligand Exchange for quantum dot structures 0.235 g ofconcentration-adjusted CdSe stock from Example 2 are exposed to areactive exchange chemical, trimethylsilylpyrollidine (TMS-Pyr), for 20minutes in an air-free environment and are mixed completely. After 20minutes, an alcohol, usually 2-propanol or methanol is added to themixture to quench the reactivity of the TMS-Pyr reagent, and toprecipitate the reactively exchanged CdSe particles. The precipitatedparticles are centrifuged at 6000 RPM for 5 minutes. The resultingsupernatant liquid is decanted and the precipitate are re-dissolved in0.235 g of anhydrous toluene for use in the procedure described inExample 2. Reactive ligand exchange is used to introduce any number ofdesired surface functionalities to the surface of quantum dot coresprior to rod growth or the surface of the core/shell particles aftersynthesis.

Example 6

Coating semiconductor nanocrystalline core/shell pairing with silicausing dioctyl sodium sulfosuccinate (AOT). Approximately 4.5 g of AOT isdissolved in 50 mL of cyclohexane. 0.5 g of QDH is precipitatedw/methanol, and then re-dissolved in hexane. 20 μL of3-aminopropyltrimethoxysilane (APTMS) is added and stirred for 30minutes. 900 μL of NH4OH (29 wt %) is added into the solutionimmediately followed by 600 μL of TEOS. The solution is stirred forabout 16 hrs which allows the mixture to react until a silica shellcoats the nanocrystal. The silica coated particles are precipitated byMeOH and the precipitated particles are separated from the supernatantusing a centrifuge. The SiO₂ coated particles can be re-dispersed intoluene or left in cyclohexane.

Example 7

Coating a semiconductor nanocrystal with silica using IGEPAL CO-520.Approximately 4.46 g of Igepal CO-520 (Polyoxyethylene (5)nonylphenylether) is dissolved in 50 mL of cyclohexane and allowed tomix. “n” may be 3, 4, 5, 6, 7, 8, 9 or 10, preferably about 5. 0.5 gramsof quantum dots dissolved in toluene are added. 20 μL of 3-APTMS isadded and stirred for about 30 minutes. 900 μL of NH₄OH (29 wt %) isadded into the solution immediately followed by 600 μL of TEOS. Thesolution is stirred for about 16 hrs at 1600 rpm which allows themixture to react until a silica shell coats the nanocrystal. Themicelles are broken up by IPA and collected using a centrifuge. The SiO₂coated particles may be re-dispersed in toluene or left in cyclohexanefor polymer integration.

Example 8

Methoxy silane coupling agent. Silica-shelled core-shell quantum dotsare dispersed in 20 parts toluene to 1 part (MeO)3SiR (R=allyl orvinyl), and constantly stirred to allow the coupling reaction to takeplace. The functionalized particles are separated and cleaned byprecipitation with IPA and centrifugation at 6000 rpm for 10 min. Theprocess is repeated two or more times. Cleaned particles are dispersedin a known amount of toluene or polymer solution.

Example 9

Quantum dot/polymer preparation. To prepare the films, a known mass ofquantum dots in toluene or cyclohexane is added to premade polymersolution, depending on solvent compatibility of the polymer matrix used.Other solvents may also be used for dissolution, if so desired forpolarity match with the matrix or to increase or decrease the viscosityor rate of solvent evolution from the cast film.

Example 10

Film casting. The composite compositions are prepared by drop castingapproximately 360 μL of QDH polymer solution onto a 12 mm glass round.The amount of quantum dots added to the polymer solution can be adjustedfor different optical densities in the final QDH film. After castingfilms, the slow evaporation of solvent is important to give a film freeof large surface imperfections. QDH-polymer solutions in toluene areallowed to evaporate in a vented fume hood. The films are cast on alevel stainless plate. Once films are dried they are analyzed for PLQYand UV-Vis properties.

Example 11

The surface of silica-shelled quantum dot was functionalized using avariety of methoxy and ethoxy silanes: (MeO)₃SiAllyl, (MeO)₃SiVinyl,(MeO)₂SiMeVinyl, (EtO)₃SiVinyl, EtOSi(Vinyl)₃. The functionalizedsilica-shelled quantum dot was then used in the standard polymerformulation with additives for crosslinking, as well as without anyfurther crosslinking co-agents such as TAIC in the case of EVA ordivinylsilanes for siloxanes.

Example 12

In one embodiment, it is preferred that the olefin group is able toparticipate in a crosslinking process through radical mechanism in thecase of EVA or through hydrosilylation process in the case of siloxanes.Allyl and vinyl are preferred, but other olefins can be included.

Example 13

In one embodiment, the degree of crosslinking may be increased usingquantum dots with a higher density of the olefin groups on silicasurface of quantum dots.

Example 14

Using polarity. The surface of a silica-shelled particle is modifiedwith organo-substituted silanes in order to maximize the compatibilitywith a polymer matrix such as the polysiloxanes for LEDs. The silicasurface is modified with organo-substituted silanes, and its propertiesare therefore modified by the grafted functional groups.

Example 15

Pt catalyst. A platinum-based catalyst may be introduced in Examples9-14. In addition to the functionalized silica particles, two competingor complementary catalysts are available for cross-linking.

Example 16

Thiol catalyst. The Pt catalyst of example 15 is replaced with a thiolcatalyst with a thiol-ene reaction. Di-thiols or multifunctional thiolsare used. The approach enables UV curing in place of heat curing.

Example 17

Synthesis of Ternary CdSe_(n)S_(n-1) QD seeds Trioctylphosphine oxide(TOPO), octadecylphosphonic acid (ODPA), oleylamine (OLAM), and cadmiumoxide (CdO) were added into a three-neck roundbottom flask with athermocouple probe, air condenser, and rubber septum. Under argon flow,the mixture was stirred and heated to 120° C. 1 mL toluene was added,and then the temperature was increased to 300° C. and then held for 60minutes. The temperature was decreased to 130° C., and the vessel wasevacuated until the foreline pressure decreased to at or below 50milliTorr. The flask was purged with argon, and then the temperature wasincreased to 320° C., after which trioctylphosphine (TOP) was injectedvia syringe. The reaction solvent was heated to between 365° C. and 370°and held for a 60-minute dwell time. The heat was turned off, and amixture of trioctylphosphine selenide (TOPSe) and sulfur oleylamine(SOLAM) was rapidly injected after the temperature dropped to 365° C.After 30 seconds, the heating mantle and glass wool were removed and thereaction vessel was cooled down by flowing compressed air on the outsideof the glass while stirring. The resulting reaction product wasprocessed by standard procedures common in the field.

In certain embodiments, general modifications to Example 17 include oneor more of (1) injecting at 320° C. and growing the nanoparticlesbetween 280-320° C., (2) changing injection and growth temperaturesanywhere between 280 and 370° C., (3) changing the sulfur to seleniumratios to tune the spectroscopic properties of the particles and modifythe particle make-up and size properties, and/or (4) using differentchalcogen (sulfur and/or selenium) precursors [e.g., chalcogenalkylamines, chalcogen alkenylamines (e.g., sulfur oleylamine),chalcogen alkenes (e.g., sulfur octadecene), chalcogen alkanes,trialkylphosphine chalcogenides (e.g., trioctylphosphine selenide,trioctylphosphine sulfide, and tributylphosphine sulfide),triarylphosphine chalcogenides (e.g., triphenylphosphine sulfide),dialkylphosphine chalcogenides (e.g., dioctylphosphine sulfide),diarylphosphine chalcogenides (e.g., diphenylphosphine sulfide), alkylchalcogenols (e.g., dodecanethiol), dialkyl dichalcogenides (didodecanedisulfide and dibenzyl diselenide), and bis(trialkylsilyl) chalcogenides(e.g., bis(trimethylsilyl) sulfide and bis(trimethylsilyl) selenide)].

Example 18

Synthesis of high quality ternary CdSe_(n)S_(n-1) QD seeds for use inhigh performance nano-sized, semiconducting heterostructures. 1.120 g ofODPA solid was added to a 3-neck 100 ml round-bottom flask and 12 g TOPOsolid was added to the flask. 0.120 g of CdO solid was added to theflask. With the flask sealed and the reagents inside (CdO, ODPA, TOPO),the reaction was heated to 120° C. under flowing UHP Argon gas. When thereaction mixture became liquid, stirring was begun at 800 RPM tocompletely distribute the CdO and ODPA. When the temperatureequilibrated at around 120° C., degassing of the reaction mixture wasbegun: Standard degas was for 30 minutes at as low a vacuum as thesystem can maintain, preferably between 10-30 torr. After the firstdegas, the reaction is switched back to flowing UHP Argon gas. Thetemperature of the reaction was raised to 280° C. to dissociate the CdO.Dissociation was accompanied by a loss of the typical red color for CdO.After dissociation of the CdO, the reaction was cooled to 120° C. forthe second degassing step. Preferably, the cooling is performed slowly.In one embodiment, the cooling was performed in increments of 40 degreeswith allowing for equilibration at each step. When the reaction mixturecooled to about 120° C., the second degassing step was begun. The seconddegassing was typically 1 hour at the lowest vacuum level possible.After the second degassing, the reaction was switched back to flowingUHP Argon. The reaction mixture was then heated. 6.0 g TOP was injectedinto the reaction solution as the temperature increased above 280° C.The reaction solution was equilibrated at 370° C. When the reaction wasequilibrated at 370° C., a mixed solution of 0.40 g of 14 w % Se:TOP and1.82 g of 7.4 w % S:TOP stock solution was injected into the solution.The reaction was run in one embodiment for 400 seconds to achieve a 510nm 1st exciton peak. To stop the reaction: while continuing to stir andflow UHP Argon through the reaction, the solution was rapidly cooled byblowing nitrogen on the outside of the flask. When the reactiontemperature was around 80° C., the reaction solution was exposed to airand approximately 6 mL of toluene was injected. The nanocrystals wereprecipitated through the addition of 2-propanol (IPA) to the reactionsolutions. Preferably the mixture should be approximately 50/50 (byvolume) reaction solution/IPA to achieve the desired precipitation.Centrifuge was performed for 5 minutes at 6000 RPM. The CdSe wasredissolved in as little toluene as possible solid (<2 mL). Nanocrystalswere precipitated again using IPA. Centrifuge was then performed. Thesupernatant liquid was decanted. The solid was dissolved in anhydroustoluene.

Example 19

Synthesis of high quality ternary CdSenSn-1 QD seeds for use in highperformance nano-sized, semiconducting heterostructures (using sulfur inallylamine). The same protocol as Example 18 was followed. However, whenthe reaction was equilibrated at 370° C., a mixed solution of (0.40 g of14 w % Se:TOP and 0.80 g of 6.5 w % sulfur in allylamine) stock solutionwas injected into the solution. The protocol of Example 18 was followedto complete the reaction and isolate the quantum dots.

Example 20

Synthesis of high quality ternary CdSe_(n)S_(n-1) QD seeds for use inhigh performance nano-sized, semiconducting heterostructures (usingsulfur in octadecene). The same protocol as Example 18 was followed.However, when the reaction was equilibrated at 370° C., a mixed solutionof (using 0.40 g of 14 w % Se:TOP and 0.80 g of 6.5 w % sulfur inoctadecene) stock solution was injected into the solution. The protocolof Example 18 was followed to complete the reaction and isolate thequantum dots.

Thus, alloyed nanocrystals and quantum dots having alloyed nanocrystalshave been disclosed. In accordance with an embodiment of the invention,a quantum dot includes an alloyed Group II-VI nanocrystalline core. Thequantum dot also includes a Group II-VI nanocrystalline shell having asemiconductor material composition different from the alloyed GroupII-VI nanocrystalline core. The Group II-VI nanocrystalline shell isbonded to and completely surrounds the alloyed Group II-VInanocrystalline core.

What is claimed is:
 1. A semiconductor structure, comprising: ananocrystalline core comprising a first semiconductor material, thefirst semiconductor material having a first bandgap; and ananocrystalline shell comprising a second semiconductor materialdifferent than the first semiconductor material at least partiallysurrounding the nanocrystalline core, the second semiconductor materialhaving a second bandgap greater than the first bandgap.
 2. Thesemiconductor structure of claim 1 further comprising: an outernanocrystalline shell comprising a third semiconductor materialsurrounding the second semiconductor material, the third semiconductormaterial having a third bandgap greater than the first or the secondbandgap.
 3. The semiconductor structure of claim 2, wherein the thirdsemiconductor material comprises a magnesium-based semiconductormaterial, and wherein the third bandgap is greater than 2 eV.
 4. Thesemiconductor structure of claim 3, wherein the magnesium-basedsemiconductor material is selected from a group of alloys consisting of:Cd_(n)Mg_(1-n)S, Zn_(x)Mg_(1-x)Se, and Zn_(m)Mg_(1-m)S.
 5. Thesemiconductor structure of claim 1, wherein the second semiconductormaterial comprises a magnesium-based semiconductor material, and whereinthe second bandgap is a wide bandgap.
 6. The semiconductor structure ofclaim 5, wherein the magnesium-based semiconductor material comprisesmagnesium chalcogenide.
 7. The semiconductor structure of claim 6,wherein the magnesium chalcogenide is selected from a group of magnesiumchalcogenides consisting of: MgO, MgS, and MgSe.
 8. The semiconductorstructure of claim 1, wherein the first bandgap and the second bandgapare nested, and a minimal mismatch of lattice constants between the coreand shell exists.
 9. The semiconductor structure of claim 5, wherein themagnesium-based semiconductor material is selected from a group ofalloys consisting of: Cd_(n)Mg_(1-n)S, Zn_(x)Mg_(1-x)Se, andZn_(m)Mg_(1-m)S.
 10. The semiconductor structure of claim 9, wherein thefirst semiconductor material is selected from a group consisting of:CdSe, and CdSe_(m)S_(m-1).
 11. The semiconductor structure of claim 1,wherein the second semiconductor material exhibits a bandgap, and abandgap alignment with the first semiconductor material, to realize aType I heterojunction bandgap alignment with the first semiconductormaterial.
 12. The semiconductor structure of claim 1, wherein thesemiconductor structure is a Type I electronic structure, in whichabsorption is substantially controlled by the nanocrystalline shell, andan emission peak is substantially controlled by the nanocrystallingcore.
 13. The semiconductor structure of claim 12, wherein the emissionpeak is further controlled by a size of the nanocrystalling core, andsize of the nanocrystalline shell.
 14. The semiconductor structure ofclaim 13, wherein the emission peak further controlled by the size ofthe nanocrystalline shell comprises the emission peak controlled by adiameter and a length of the nanocrystalline shell.
 15. A quantum dot,comprising: a ternary semiconductor nanocrystalline shell made of afirst Group II-VI semiconductor material selected from a groupconsisting of: CdMgS, ZnMgSe, and ZnMgS; and a semiconductornanocrystalline core made of a second, different, Group II-VIsemiconductor material selected from the group consisting of: CdSe, andCdSe_(m)S_(1-m), the ternary semiconductor nanocrystalline shell bondedto and completely surrounding the semiconductor nanocrystalline core.16. The quantum dot of claim 15, further comprising an outer shell layerencapsulating the ternary semiconductor nanocrystalline shell.
 17. Thequantum dot of claim 15, wherein the semiconductor nanocrystalline coreis an anisotropic semiconductor nanocrystalline core.
 18. The quantumdot of claim 17, wherein the anisotropic semiconductor nanocrystallinecore has an aspect ratio between, but not including, 1.0 and 2.0.